TWI568835B

TWI568835B - Liquid-crystal display

Info

Publication number: TWI568835B
Application number: TW097133296A
Authority: TW
Inventors: 伯納茲喬格; 陶格貝克安德烈斯
Original assignee: 馬克專利公司
Priority date: 2007-08-30
Filing date: 2008-08-29
Publication date: 2017-02-01
Also published as: WO2009030329A1; JP2010537256A; CN101790573B; CN103820126B; JP5595915B2; EP2181173A1; KR101498750B1; JP6117085B2; TW200920821A; CN101790573A; EP2181173B1; ATE547502T1; US8304035B2; JP2014112226A; KR20100070338A; CN103820126A; TW201536899A; US20100309423A1; DE102008036248A1

Abstract

The present invention relates to a liquid-crystal (LC) display of the PS (polymer stabilized) or PSA (polymer sustained alignment) type, and to polymerisable compounds and LC media for use in PS (polymer stabilized) and PSA displays.

Description

液晶顯示器LCD Monitor

本發明係關於PSA(聚合物持久對準)型液晶(LC)顯示器，以及用於PSA顯示器的可聚合化合物及LC介質。This invention relates to PSA (Polymer Aligned) liquid crystal (LC) displays, as well as polymerizable compounds and LC media for PSA displays.

本發明係關於PS(聚合物穩定化)型或PSA(聚合物持續對準)型液晶(LC)顯示器，以及用於PS(A)顯示器的新穎可聚合化合物及新穎LC介質。This invention relates to PS (Polymer Stabilized) or PSA (Polymer Aligned) Liquid Crystal (LC) displays, as well as novel polymerizable compounds and novel LC media for PS (A) displays.

目前使用的液晶顯示器(LC顯示器)主要為TN型(扭轉向列型)液晶顯示器。然而，該等液晶顯示器具有對比度之強視角依賴性的缺點。Currently used liquid crystal displays (LC displays) are mainly TN type (twisted nematic) liquid crystal displays. However, such liquid crystal displays have the disadvantage of strong contrast dependence of contrast.

此外，已知具有更寬視角的所謂VA(垂直對準型)顯示器。VA顯示器之LC單元在兩個透明電極之間含有LC介質層，其中LC介質一般具有負電介質(DC)各向異性值。在關斷狀態下，LC層之分子與電極表面垂直對準(各向同性)或具有傾斜的各向同性對準取向。向電極施加電壓時，LC分子發生重新對準而與電極表面平行。Further, a so-called VA (Vertical Alignment Type) display having a wider viewing angle is known. The LC cell of the VA display contains an LC dielectric layer between the two transparent electrodes, wherein the LC medium typically has a negative dielectric (DC) anisotropy value. In the off state, the molecules of the LC layer are vertically aligned (isotropic) with the electrode surface or have an oblique isotropic alignment orientation. When a voltage is applied to the electrodes, the LC molecules are realigned to be parallel to the electrode surface.

此外，已知OCB(光學補償彎曲型)顯示器，其係基於雙折射效應及具有LC層，該LC層具有所謂的"彎曲"對準取向及一般具有正(DC)各向異性。施加電壓時，LC分子發生重新對準而垂直於電極表面。此外，OCB顯示器一般含有一或多層雙折射光學延遲膜，以防止彎曲單元在黑暗狀態下發生非所要之透光。與TN顯示器相比，OCB顯示器具有更寬的視角及更短的響應時間。Furthermore, OCB (Optically Compensatory Bend) displays are known which are based on birefringence effects and have an LC layer with a so-called "bend" alignment orientation and generally positive (DC) anisotropy. When a voltage is applied, the LC molecules are realigned perpendicular to the electrode surface. In addition, OCB displays typically contain one or more layers of birefringent optical retardation film to prevent undesired light transmission of the bending unit in the dark. Compared to TN displays, OCB displays have a wider viewing angle and shorter response times.

亦已知IPS(共平面切換型)顯示器，其在兩基板之間含有LC層，兩基板中僅一者具有電極層，該電極層結構一般為梳形。從而在施加電壓時，形成具有平行於LC層之顯著分量的電場。由此促使層平面中之LC分子之重新對準。此外，已提出所謂的FFS(邊緣場切換型)顯示器(尤其參見S.H.Jung等人，Jpn.J.Appl.Phys.，第43 卷，第3期，2004,1028)，其亦含有位於相同基板上的兩個電極，但與IPS顯示器相比，該等電極中僅一者呈結構化(梳形)電極形式，而另一電極為非結構化電極。從而形成所謂的強"邊緣場"(亦即，靠近電極邊緣的強電場)及整個單元內的具有強垂直分量與強水平分量的電場。IPS顯示器與FFS顯示器皆具有對比度之低視角依賴性。An IPS (coplanar switching type) display is also known which includes an LC layer between two substrates, and only one of the two substrates has an electrode layer, and the electrode layer structure is generally comb-shaped. Thereby, when a voltage is applied, an electric field having a significant component parallel to the LC layer is formed. This promotes realignment of the LC molecules in the plane of the layer. Furthermore, a so-called FFS (Fringe Field Switching Type) display has been proposed (see especially SHJung et al., Jpn. J. Appl. Phys., Vol. 43 , No. 3, 2004, 1028), which also contains the same substrate. The two electrodes, but compared to the IPS display, only one of the electrodes is in the form of a structured (comb) electrode and the other electrode is an unstructured electrode. Thereby a so-called strong "fringe field" (i.e., a strong electric field near the edge of the electrode) and an electric field having a strong vertical component and a strong horizontal component in the entire cell are formed. Both IPS displays and FFS displays have low viewing angle dependence of contrast.

在更新型的VA顯示器中，LC分子之一致對準被限於LC單元內之複數個較小域中。該等域之間可能存在向錯，亦稱斜域。與習知VA顯示器相比，具有斜域的VA顯示器具有對比度及灰影之更大視角獨立性。此外，由於不再需要藉由例如摩擦對電極表面進行額外處理以便分子在接通狀態下之一致對準，因此此類型顯示器製造更簡單。實情為，藉由特殊的電極設計可控制較佳的傾角或預傾角方向。在所謂的MVA(多域垂直對準型)顯示器中，此一般藉由具有導致局部預傾斜之突起的電極達成。從而，在施加電壓時，LC分子與單元之不同限定區域中之不同方向之電極表面平行對準。從而達成"受控"切換，且防止形成干擾性向錯線。儘管此排列改良顯示器之視角，但其導致其透光性降低。MVA之進一步發展係在僅一電極側上使用突起，而對側電極具有狹縫，從而改良透光性。施加電壓時，開縫電極在LC單元中形成非均一電場，意謂受控切換仍可達成。為進一步改良透光性，可增加狹縫與突起之間的間距，然而此舉又導致響應時間延長。在所謂的PVA(圖案化VA)中，經由相反兩側上的狹縫將兩電極結構化而使得突起完全冗餘，從而形成經增強之對比度及經改良之透光性，然而在技術上困難且使得顯示器對機械影響(拍打等)更敏感。對於很多應用，諸如監視器及尤其TV螢幕，需要縮短響應時間及改良顯示器之對比度及亮度(透光度)。In a newer VA display, consistent alignment of LC molecules is limited to a plurality of smaller domains within the LC cell. There may be disclination between these domains, also known as the oblique domain. Compared to conventional VA displays, VA displays with oblique domains have greater viewing angle independence of contrast and gray shading. Furthermore, this type of display is simpler to manufacture since it is no longer necessary to perform additional processing on the electrode surface by, for example, friction so that the molecules are aligned in an on state. The truth is that the preferred tilt or pretilt direction can be controlled by a special electrode design. In so-called MVA (Multi-Domain Vertical Alignment) displays, this is typically achieved by electrodes having protrusions that cause local pre-tilt. Thus, when a voltage is applied, the LC molecules are aligned in parallel with the electrode surfaces in different directions in different defined regions of the cell. Thereby achieving a "controlled" switching and preventing the formation of disturbing disclination lines. Although this arrangement improves the viewing angle of the display, it leads to its penetration. Light is reduced. Further development of MVA uses protrusions on only one electrode side, and the opposite side electrodes have slits to improve light transmittance. When a voltage is applied, the slit electrode forms a non-uniform electric field in the LC cell, meaning that controlled switching is still achievable. In order to further improve the light transmittance, the distance between the slit and the protrusion can be increased, but this also leads to an increase in response time. In the so-called PVA (Patternized VA), the two electrodes are structured via slits on opposite sides to make the protrusions completely redundant, thereby forming enhanced contrast and improved light transmission, but technically difficult And make the display more sensitive to mechanical influences (beating, etc.). For many applications, such as monitors and especially TV screens, it is desirable to reduce response time and improve display contrast and brightness (transparency).

另一發展為所謂的PS(聚合物穩定化)顯示器，其亦已以術語"PSA"(聚合物持續對準)為人所知。在該等顯示器中，將少量(例如0.3 wt%，通常<1 wt%)可聚合化合物添加至LC介質中，且在引入LC單元內之後，在電極間施加電壓下，通常藉由UV光聚作用就地聚合或交聯。將可聚合液晶原性或液晶化合物(亦稱"反應性液晶原"(RM))添加至LC混合物中已證明特別適當。Another development is the so-called PS (Polymer Stabilized) display, which has also been known by the term "PSA" (polymer continuous alignment). In such displays, a small amount (eg, 0.3 wt%, typically <1 wt%) of the polymerizable compound is added to the LC medium and, after introduction into the LC cell, is typically applied by UV light at a voltage applied between the electrodes. The effect is to polymerize or crosslink in situ. The addition of polymerizable liquid crystals or liquid crystal compounds (also known as "reactive liquid crystals" (RM)) to the LC mixture has proven to be particularly suitable.

同時，PS或PSA原理正用於各種傳統的LC顯示器。從而已知例如PSA－VA、PSA－OCB、PS－IPS及PS－TN顯示器。如測試單元所證明，PSA方法形成單元內之預傾斜。因此，在PSA－OCB顯示器之情況下，可使彎曲結構穩定化，以使得補償電壓不需要或可降低。在PSA－VA顯示器之情況下，此預傾斜對響應時間具有正面效果。對於PSA－VA顯示器，可使用標準的MVA或PVA像素及電極布置。然而，此外可經由例如僅一側電極結構化且無突起來達成，從而使製造大大簡化並且同時在形成優良對比度的同時形成優良透光性。At the same time, the PS or PSA principle is being used in a variety of conventional LC displays. Thus, for example, PSA-VA, PSA-OCB, PS-IPS, and PS-TN displays are known. As evidenced by the test unit, the PSA method forms a pretilt within the unit. Therefore, in the case of a PSA-OCB display, the curved structure can be stabilized so that the compensation voltage is not required or can be lowered. In the case of a PSA-VA display, this pre-tilt has a positive effect on response time. For PSA-VA display The display can be used with standard MVA or PVA pixels and electrode arrangements. However, it can also be achieved, for example, by structuring only one side of the electrode and without protrusions, thereby greatly simplifying the manufacturing and simultaneously forming excellent light transmittance while forming excellent contrast.

PSA－VA顯示器描述於例如以下文獻中：JP 10－036847 A、EP 1 170 626 A2、EP 1 378 557 A1、EP 1 498 468 A1、US 2004/0191428 A1、US 2006/0066793 A1及US 2006/0103804 A1。PSA－OCB顯示器描述於例如以下文獻中：T.－J－Chen等人，Jpn.J.Appl.Phys.45,2006,2702－2704及S.H.Kim,L.－C－Chien,Jpn.J.Appl.Phys.43,2004,7643－7647。PS－IPS顯示器描述於例如US 6,177,972及Appl.Phys.Lett.1999,75(21),3264中。PS－TN顯示器描述於例如Optics Express 2004,12(7),1221中。PSA-VA displays are described, for example, in the following documents: JP 10-036847 A, EP 1 170 626 A2, EP 1 378 557 A1, EP 1 498 468 A1, US 2004/0191428 A1, US 2006/0066793 A1 and US 2006/ 0103804 A1. PSA-OCB displays are described, for example, in the following documents: T.-J-Chen et al, Jpn. J. Appl. Phys. 45, 2006, 2702-2704 and SHKim, L.-C-Chien, Jpn. J. Appl. Phys. 43, 2004, 7643-7647. PS-IPS displays are described, for example, in US 6,177,972 and Appl. Phys. Lett. 1999, 75(21), 3264. PS-TN displays are described, for example, in Optics Express 2004, 12(7), 1221.

然而，已發現，獲知於先前技術的LC混合物及RM在用於PS(A)顯示器中時仍具有某些缺點。因此，決非每種所要溶解性單體皆適用於PS(A)顯示器，且似乎難以找到比僅使用預傾角量測之直接PSA實驗更適宜的選擇標準。若需要聚合經由UV光來進行而不添加光引發劑(此對於有些應用可能有利)，則選擇餘地變得更小。此外，LC混合物之所選"材料系統"(以下亦稱"LC主體混合物")＋可聚合組分應具有可能的最好的電特性，尤其是高的"電壓保持比"(HR或VHR)。However, it has been found that LC mixtures and RMs known in the prior art still have certain disadvantages when used in PS (A) displays. Therefore, not every desired soluble monomer is suitable for PS(A) displays, and it seems difficult to find a selection criterion that is more suitable than direct PSA experiments using only pretilt measurements. If polymerization is required to be carried out via UV light without the addition of a photoinitiator (which may be advantageous for some applications), the margin of choice becomes smaller. In addition, the selected "material system" (hereinafter also referred to as "LC host mixture") + polymerizable component of the LC mixture should have the best possible electrical properties, especially a high "voltage holding ratio" (HR or VHR). .

先前技術中所揭示之PS(A)顯示器一般含有其中所有可聚合基團與液晶原性之環系統直接連接(亦即無間隔基)的 RM(無間隔基RM)。EP 1 498 468 A1提出例如其中LC混合物包含選自以下式之RM的PSA－VA顯示器：其中P¹ 及P² 表示可聚合基團，例如丙烯酸酯、甲基丙烯酸酯、乙烯基、乙烯氧基或環氧化物基團。EP 1 498 468 A1報導，使用該等"無間隔基RM"能夠達成經改良之顯示器特性，諸如更低的"影像燒傷"。The PS(A) displays disclosed in the prior art generally contain RM (without spacer RM) in which all of the polymerizable groups are directly attached to the liquid crystal intrinsic ring system (i.e., without spacers). EP 1 498 468 A1 proposes, for example, a PSA-VA display in which the LC mixture comprises an RM selected from the following formula: Wherein P ¹ and P ² represent a polymerizable group such as an acrylate, methacrylate, vinyl, vinyloxy or epoxide group. EP 1 498 468 A1 reports that improved "display-free features" such as lower "image burns" can be achieved using these "no spacer RM".

此外，EP 1 498 468 A1報導，相比之下，其中兩個可聚合基團經由間隔基(例如柔性伸烷基間隔基)與液晶原性連接的RM，諸如下式之RM：較不適用於PSA－VA顯示器。Furthermore, EP 1 498 468 A1 reports, by contrast, an RM in which two polymerizable groups are connected to a liquid crystal via a spacer (for example a flexible alkylene spacer), such as RM of the formula: Less suitable for PSA-VA displays.

然而，無間隔基的RM(如上述式之彼等RM)一般具有高熔點且在多種常見的LC混合物中僅具有有限的溶解度且因此往往傾向於自發地自混合物中結晶析出。此外，自發聚合之風險妨礙了為溶解可聚合組分而將LC主體混合物溫熱，此意謂需要甚至在室溫下具有可能最佳的溶解性。此外，在例如將LC介質引入LC顯示器中時存在離析(層析效應)的風險，此會大大損害顯示器之均質性。此問題由於以下事實而進一步加劇：LC介質一般在低溫下引入以便減小自發聚合之風險(參見上文)，而低溫又對溶解性具有不利影響。However, spacer-free RMs (such as the RM of the above formula) generally have a high melting point and have only limited solubility in a variety of common LC mixtures and thus tend to spontaneously precipitate out of the mixture spontaneously. Furthermore, the risk of spontaneous polymerization prevents the LC host mixture from being warmed to dissolve the polymerizable component, which means that there is a need for even the best solubility even at room temperature. Furthermore, there is a risk of segregation (chromatography effect), for example when introducing an LC medium into an LC display, which can greatly impair the homogeneity of the display. This problem is further exacerbated by the fact that LC media are generally introduced at low temperatures in order to reduce the risk of spontaneous polymerization (see above), while low temperatures have no solubility Benefits.

因此對於不具有上述缺陷或僅具有很小上述缺陷且具有經改良之特性的PS(A)顯示器、尤其VA型及OCB型之PS(A)顯示器，及用於該等顯示器的LC介質及RM仍存在更大需求。特定而言，對於具有低溫下之抗離析高穩定性、高比電阻、同時具有大工作溫度範圍、短響應時間(甚至在低溫下)及低臨限電壓、從而促成大量灰影、高對比度及寬視角且在UV曝光後具有高電壓保持比(HR)值的PS(A)顯示器以及用於該等顯示器的LC介質及RM存在很大需求。Therefore, PS (A) displays, and VA type and OCB type PS (A) displays, which do not have the above defects or have only the above-mentioned defects and have improved characteristics, and LC media and RM for the displays There is still a greater demand. In particular, it has high stability against segregation at low temperatures, high specific resistance, large operating temperature range, short response time (even at low temperatures) and low threshold voltage, resulting in a large amount of gray shadow, high contrast and PS (A) displays with wide viewing angles and high voltage hold ratio (HR) values after UV exposure, as well as LC media and RM for such displays, are in great demand.

本發明係基於提供不具有上述缺陷或僅具有較小上述缺陷、能夠設定預傾角且較佳同時具有很高比電阻值、低臨限電壓及短響應時間之PS(A)顯示器之目標。The present invention is based on the object of providing a PS(A) display which does not have the above-mentioned defects or which has only the above-mentioned defects, can set a pretilt angle, and preferably has a high specific resistance value, a low threshold voltage, and a short response time.

現已意外發現，此目標可藉由使用本發明之PS(A)顯示器達成，該等PS(A)顯示器包含含有液晶原性及兩個或兩個以上聚合基團的聚合化合物(RM)，該等聚合基團中至少一者經由間隔基與液晶原性連接且其中至少一者直接與液晶原性連接(亦即無間隔基)。與先前技術相比，本發明之RM之優勢為因間隔基之引入所達成之更低熔點、極低結晶傾向及在多種可市購LC主體混合物中經改良之溶解度。此外，本發明之LC介質仍呈現足夠的傾角，經由對VA傾角量測單元之預傾角量測，已結合LC介質證明此。特定而言，可在不添加光引發劑的情況下達成預傾角。It has been surprisingly discovered that this object can be achieved by using the PS(A) display of the present invention comprising a polymeric compound (RM) containing liquid crystal origin and two or more polymeric groups, At least one of the polymeric groups is attached to the liquid crystal via a spacer and at least one of them is directly attached to the liquid crystal (ie, without a spacer). The advantages of the RM of the present invention over the prior art are the lower melting point achieved by the introduction of the spacer, the very low crystallization tendency, and the improved solubility in a variety of commercially available LC host mixtures. Furthermore, the LC medium of the present invention still exhibits a sufficient tilt angle, as evidenced by the LC medium combined with the pretilt angle measurement of the VA tilt measurement unit. In particular, the pretilt angle can be achieved without the addition of a photoinitiator.

本發明因此係關於含有LC單元的PS(聚合物穩定化)或PSA(聚合物持續對準)型液晶(LC)顯示器，該LC單元係由以下組成：兩個基板，其中至少一基板可透光且至少一基板具有電極層；及一定位於該等基板之間、包含聚合組分及低分子量組分的LC介質層，其中該聚合組分可藉由在施加電壓下、使LC介質中之一或多種可聚合化合物在LC單元之基板之間聚合而獲得，該顯示器特徵在於，該等可聚合化合物中至少一者含有液晶原性及兩個或兩個以上可聚合基團，其中至少一可聚合基團經由間隔基與液晶原性連接且其中至少一可聚合基團不經由間隔基(亦即直接)與液晶原性連接。The present invention is therefore directed to a PS (Polymer Stabilized) or PSA (Polymer Aligned) Liquid Crystal (LC) display containing LC cells consisting of two substrates, at least one of which is permeable Light and at least one substrate having an electrode layer; and an LC dielectric layer between the substrates, comprising a polymeric component and a low molecular weight component, wherein the polymeric component can be made in the LC medium by applying a voltage Obtaining one or more polymerizable compounds between substrates of the LC unit, the display characterized in that at least one of the polymerizable compounds contains liquid crystal originality and two or more polymerizable groups, at least one of which The polymerizable group is attached to the liquid crystal via a spacer and wherein at least one polymerizable group is not attached to the liquid crystal without via a spacer (ie, directly).

尤其較佳為其中聚合組分完全由一或多種含有液晶原性及兩個可聚合基團之可聚合化合物組成的LC顯示器，其中一可聚合基團經由間隔基與液晶原性連接且其中一可聚合基團不經由間隔基與液晶原性連接。Particularly preferred is an LC display in which the polymeric component consists entirely of one or more polymerizable compounds comprising a liquid crystal former and two polymerizable groups, wherein a polymerizable group is attached to the liquid crystal via a spacer and one of The polymerizable group is not attached to the liquid crystal without via a spacer.

本發明此外係關於如上文及下文所述的新穎可聚合化合物(反應性液晶原或"RM")。The invention further relates to novel polymerizable compounds (reactive mesogens or "RM") as described above and below.

本發明此外係關於包含一或多種如上文及下文所述之可聚合化合物的LC介質。The invention further relates to LC media comprising one or more polymerizable compounds as described above and below.

本發明此外係關於包含以下各者的LC介質：－包含一或多種如上文及下文所述之可聚合化合物的可聚合組分A)；－包含一或多種、較佳兩種或兩種以上低分子量(亦即單體或非聚合)化合物的液晶組分B)，下文亦稱為"LC主體混合物"。The invention further relates to an LC medium comprising: - a polymerizable component A) comprising one or more polymerizable compounds as described above and below; - comprising one or more, preferably two or more Liquid crystal component B) of low molecular weight (ie monomeric or non-polymeric) compounds, hereinafter also referred to as "LC body mixing Compound".

本發明此外係關於如上文及下文所述之可聚合化合物在PS及PSA顯示器中的用途。The invention further relates to the use of polymerizable compounds as described above and below in PS and PSA displays.

本發明此外係關於含有本發明之一或多種如上文及下文所述之化合物或LC介質的LC顯示器，尤其為PS或PSA顯示器，尤其較佳為PSA－VA、PSA－OCB、PS－IPS、PS－FFS或PS－TN顯示器。The invention further relates to an LC display comprising one or more of the compounds or LC media of the invention as described above and below, in particular a PS or PSA display, particularly preferably PSA-VA, PSA-OCB, PS-IPS, PS-FFS or PS-TN display.

尤其較佳為包含一、二或三種如上文及下文所述之可聚合化合物的LC介質。Especially preferred are LC media comprising one, two or three polymerizable compounds as described above and below.

此外較佳為其中可聚合組分A)完全由如上文及下文所述之可聚合化合物組成的LC介質。Further preferred are LC media in which the polymerizable component A) consists entirely of polymerizable compounds as described above and below.

此外較佳為其中組分B)為具有向列型液晶相之LC化合物或LC混合物的LC介質。Further preferred is an LC medium in which component B) is an LC compound or a mixture of LCs having a nematic liquid crystal phase.

尤其較佳為含有具有二、三或四個烴環之液晶原性的可聚合化合物，該等烴環選自五員環或六員環、亦可稠合且亦可含有一或多個雜原子。Particularly preferred is a polymerizable compound containing a liquid crystal original having two, three or four hydrocarbon rings selected from a five-membered ring or a six-membered ring, which may also be fused and may also contain one or more impurities. atom.

此外較佳為其中液晶原性恰好在一位置經由間隔基且恰好在一位置不經由間隔基與可聚合基團連接的可聚合化合物。Further preferred is a polymerizable compound in which the liquid crystal is bonded to the polymerizable group at a position just via a spacer at a position and not via a spacer.

此外較佳為非對掌性可聚合化合物及包含非對掌性化合物、較佳完全由非對掌性化合物組成的LC介質。Further preferred are non-pivotic polymerizable compounds and LC media comprising a non-pivotic compound, preferably consisting entirely of non-preferable compounds.

可聚合化合物可單獨添加至LC介質中，但亦可使用包含兩種或兩種以上本發明之可聚合化合物的混合物。將此類混合物聚合時，形成共聚物。本發明此外係關於上文及下文所述的可聚合混合物。可聚合化合物可為液晶原性或非液晶原性化合物。The polymerizable compound may be added to the LC medium alone, but a mixture comprising two or more kinds of the polymerizable compounds of the present invention may also be used. When such a mixture is polymerized, a copolymer is formed. The present invention is also related to the above and A polymerizable mixture as described below. The polymerizable compound may be a liquid crystalline or non-liquid crystalline compound.

在本發明之一較佳實施例中，可聚合化合物選自式I：P^a －Sp－A¹ －(Z¹ －A² )_m1 －P^b I其中個別基團具有以下含義：P^a 及P^b 彼此獨立地各自表示可聚合基團；Sp表示間隔基；A¹ 及A² 彼此獨立地各自表示較佳具有4至25個C原子、亦可含有稠環且亦可經L單取代或多取代的芳族、雜芳族、脂環族或雜環基團；L表示H、OH、鹵素、SF₅ 、NO₂ 、碳基團或烴基團；Z¹ 在各自出現時相同或不同地表示－O－、－S－、－CO－、－CO－O－、－OCO－、－O－CO－O－、－OCH₂ －、－CH₂ O－、－SCH₂ －、－CH₂ S－、－CF₂ O－、－OCF₂ －、－CF₂ S－、－SCF₂ －、－(CH₂ )_n1 －、－CF₂ CH₂ －、－CH₂ CF₂ －、－(CF₂ )_n1 －、－CH＝CH－、－CF＝CF－、－C≡C－、－CH＝CH－COO－、－OCO－CH＝CH－、CR⁰ R⁰⁰ 或單鍵；R⁰ 及R⁰⁰ 彼此獨立地各自表示H或具有1至12個C原子的烷基；m1表示0、1、2、3或4；n1表示1、2、3或4。In a preferred embodiment of the invention, the polymerizable compound is selected from the group consisting of Formula I: P ^a -Sp-A ¹ -(Z ¹ -A ² ) _m1 -P ^b I wherein each group has the following meaning: P ^a and P ^b each independently represents a polymerizable group; Sp represents a spacer; A ¹ and A ² each independently represent preferably 4 to 25 C atoms, may also contain a fused ring, and may also be monosubstituted by L or a polysubstituted aromatic, heteroaromatic, alicyclic or heterocyclic group; L represents H, OH, halogen, SF ₅ , NO ₂ , a carbon group or a hydrocarbon group; Z ¹ is the same or different when each appears Expresses -O-, -S-, -CO-, -CO-O-, -OCO-, -O-CO-O-, -OCH ₂ -, -CH ₂ O-, -SCH ₂ -, -CH ₂ S-, -CF ₂ O-, -OCF ₂ -, -CF ₂ S-, -SCF ₂ -, -(CH ₂ ) _n1 -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -(CF ₂ ) _n1 -, -CH=CH-, -CF=CF-, -C≡C-, -CH=CH-COO-, -OCO-CH=CH-, CR ⁰ R ⁰⁰ or single bond; R ⁰ and R ⁰⁰ independently of one another, denote H or alkyl having 1 to 12 C atoms; M1 represents 2, 3 or 4; n1 3 or 4 are shown.

尤其較佳的式I化合物為其中A¹ 、A² 、Z¹ 、Sp及m1具有上述含義的彼等化合物，且A¹ 及A² 彼此獨立地各自表示1,4－伸苯基、萘－1,4－二基或萘－2,6－二基，此外，其中該等基團中之一或多個CH基團可經N、環己烷－1,4－二基置換；此外，其中一或多個非相鄰CH₂ 基團可經O及/或S、1,4－伸環已烯基、二環[1.1.1]戊烷－1,3－二基、二環[2.2.2]辛烷－1,4－二基、螺[3.3]庚烷－2,6－二基、哌啶－1,4－二基、十氫萘－2,6－二基、1,2,3,4－四氫萘－2,6－二基、茚滿－2,5－二基或八氫－4,7－甲橋茚滿－2,5－二基置換，其中所有該等基團可未經取代或經L單取代或多取代；L表示P－、P－Sp－、OH、CH₂ OH、F、Cl、Br、I、－CN、－NO₂ 、－NCO、－NCS、－OCN、－SCN、－C(＝O)N(R^x )₂ 、－C(＝O)Y¹ 、－C(＝O)R^x 、－N(R^x )₂ 、視需要經取代之矽烷基、具有6至20個C原子之視需要經取代之芳基，或具有1至25個C原子之直鏈或支鏈烷基、烷氧基、烷基羰基、烷氧基羰基、烷基羰氧基或烷氧基羰氧基，此外，其中一或多個H原子可經F、Cl、P－或P－Sp－置換；P表示可聚合基團；Y¹ 表示鹵素；R^x 表示P－、P－Sp－、H、鹵素、具有1至25個C原子之直鏈、支鏈或環狀烷基，此外，其中一或多個非相鄰CH₂ 基團可以O及/或S原子彼此間不直接相連之方式經－O－、－S－、－CO－、－CO－O－、－O－CO－、－O－CO－O－置換，且此外，其中一或多個H原子可經以下基團置換：F、Cl、P－或P－Sp－、具有6至40個C原子之視需要經取代之芳基或芳氧基，或具有2至40個C原子之視需要經取代之雜芳基或雜芳氧基。Particularly preferred compounds of the formula I are those in which A ¹ , A ² , Z ¹ , Sp and m1 have the abovementioned meanings, and A ¹ and A ² each independently represent 1,4-phenylene, naphthalene- a 1,4-diyl or naphthalene-2,6-diyl group, wherein, in addition, one or more CH groups of the groups may be replaced by N, cyclohexane-1,4-diyl; One or more non-adjacent CH ₂ groups may be via O and/or S, 1,4-cyclohexenylene, bicyclo[1.1.1]pentane-1,3-diyl, bicyclo [ 2.2.2] Octane-1,4-diyl, spiro[3.3]heptane-2,6-diyl, piperidin-1,4-diyl, decahydronaphthalene-2,6-diyl, 1 , 2,3,4-tetrahydronaphthalene-2,6-diyl, indane-2,5-diyl or octahydro-4,7-methyl bridge indole-2,5-diyl substitution, in which all These groups may be unsubstituted or monosubstituted or polysubstituted by L; L represents P-, P-Sp-, OH, CH ₂ OH, F, Cl, Br, I, -CN, -NO ₂ , -NCO , -NCS, -OCN, -SCN, -C(=O)N(R ^x ) ₂ , -C(=O)Y ¹ , -C(=O)R ^x , -N(R ^x ) ₂ , An optionally substituted aryl group having 6 to 20 C atoms to be substituted Or a linear or branched alkyl group having 1 to 25 C atoms, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkoxycarbonyloxy group, in addition, one or more of them The H atom may be substituted by F, Cl, P- or P-Sp-; P represents a polymerizable group; Y ¹ represents a halogen; R ^x represents P-, P-Sp-, H, halogen, having 1 to 25 C a linear, branched or cyclic alkyl group of an atom, in addition, one or more non-adjacent CH ₂ groups may be O-, -S-, in a manner in which O and/or S atoms are not directly connected to each other. -CO-, -CO-O-, -O-CO-, -O-CO-O- substitution, and further, one or more H atoms may be replaced by the following groups: F, Cl, P- or P -Sp-, an optionally substituted aryl or aryloxy group having 6 to 40 C atoms, or an optionally substituted heteroaryl or heteroaryloxy group having 2 to 40 C atoms.

尤其較佳的式I化合物選自以下子式：其中P及Sp在各自出現時相同或不同地具有上述含義，L具有上文及下文所指明之含義之一，L'及L"彼此獨立地各自表示H、F或Cl，Z在各自出現時相同或不同地具有上下文中針對Z¹ 所指明之含義之一且較佳表示－COO－、－OCO－或單鍵，x為0或1，r為0、1、2、3或4，s為0、1、2或3，且t為0、1或2。Particularly preferred compounds of formula I are selected from the following subtypes: Wherein P and Sp have the same meanings, respectively, when they occur, and L has one of the meanings indicated above and below, L' and L" each independently represent H, F or Cl, and Z in each occurrence Same or differently having ^one of the meanings indicated for Z ¹ in the context and preferably representing -COO-, -OCO- or a single bond, x being 0 or 1, r being 0, 1, 2, 3 or 4, s Is 0, 1, 2 or 3, and t is 0, 1 or 2.

其他較佳的式I化合物為含有雜環A¹ 及/或A² 的彼等物，尤其其中所存在之環A¹ 及A² 中之一或多者表示1,4－伸苯基、萘－1,4－二基或萘－2,6－二基的彼等物，其中一或多個CH基團已經N置換。尤其較佳之此類化合物選自以下子式：其中P、Sp、L、r及s具有上述含義。Other preferred compounds of formula I are those containing a heterocyclic ring A ¹ and/or A ² , especially wherein one or more of the rings A ¹ and A ² present represent 1,4-phenylene, naphthalene Or a 1,4-diyl or naphthalene-2,6-diyl group in which one or more CH groups have been replaced by N. Particularly preferred such compounds are selected from the following subtypes: Wherein P, Sp, L, r and s have the above meanings.

在上下文中所述的可聚合化合物中，L及R^x 較佳表示不為P及P－Sp的基團。Among the polymerizable compounds described in the context, L and R ^x preferably represent a group which is not P and P-Sp.

在本發明之另一較佳實施例中，式I及其子式之化合物含有一或多個含有兩種或兩種以上可聚合基團P的支鏈基團P^a －Sp(多官能可聚合基團)。適當的此類基團及含有其的可聚合化合物描述於例如US 7,060,200 B1或US 2006/0172090 A1中。尤其較佳為選自下式的多官能可聚合基團：其中：烷基表示單鍵或具有1至12個C原子的直鏈或支鏈伸烷基，此外，其中一或多個非相鄰CH₂ 基團可彼此獨立地以O及/或S原子彼此間不直接相連之方式各自經以下基團置換：－C(R^x )＝C(R^x )－、－C≡C－、－N(R^x )－、－O－、－S－、－CO－、－CO－O－、－O－CO－、－O－CO－O－，且此外，其中一或多個H原子可經F、Cl或CN置換，其中R^x 具有上述含義且較佳表示如上定義之R⁰ ；aa及bb彼此獨立地各自表示0、1、2、3、4、5或6；X具有針對X'所指明之含義之一，且 P^1－5 彼此獨立地各自具有如上針對P所指明之含義之一。In another preferred embodiment of the invention, the compound of formula I and its subformula contains one or more branched groups P ^a -Sp containing two or more polymerizable groups P (multifunctional Polymeric group). Suitable such groups and polymerizable compounds containing the same are described, for example, in US 7,060,200 B1 or US 2006/0172090 A1. Particularly preferred is a polyfunctional polymerizable group selected from the group consisting of: Wherein: alkyl represents a single bond or a straight or branched alkyl group having from 1 to 12 C atoms, and further wherein one or more non-adjacent CH ₂ groups may independently have O and/or S atoms The ways in which they are not directly connected to each other are replaced by the following groups: -C(R ^x )=C(R ^x )-, -C≡C-, -N(R ^x )-, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, and further, wherein one or more H atoms may be replaced by F, Cl or CN, wherein R ^x has the above meaning and Preferably, R ⁰ is as defined above; aa and bb each independently represent 0, 1, 2, 3, 4, 5 or 6; X has one of the meanings indicated for X', and P ^1-5 are independent of each other Each has one of the meanings indicated above for P.

上文及下文使用以下含義：除非另外指明，否則術語"PSA"用於表示PS顯示器及PSA顯示器。The following meanings are used above and below: Unless otherwise indicated, the term "PSA" is used to denote a PS display and a PSA display.

術語"液晶原性"已為熟習此項技術者所知且已描述於文獻中，且表示因其相吸及相斥性相互作用之各向異性而實質上有助於造成低分子量物質或聚合物質的液晶(LC)相的基團。含有液晶原性的化合物(液晶原性化合物)本身未必具有LC相。液晶原性化合物亦可僅在與其他化合物混合之後及/或聚合之後呈現LC相特性。典型的液晶原性為例如硬棒狀或盤狀單元。結合液晶原性或LC化合物使用的術語及定義概述於Pure Appl.Chem.73(5),888(2001)及C.Tschierske,G.Pelzl,S.Diele,Angew.Chem.2004,116,6340－6368。The term "liquid crystallinity" is known to those skilled in the art and has been described in the literature and indicates that it substantially contributes to the formation of low molecular weight species or polymerization due to the anisotropy of their phase attraction and repulsive interactions. a group of liquid crystal (LC) phases of a substance. The liquid crystal-containing compound (liquid crystal-derived compound) itself does not necessarily have an LC phase. The liquid crystal-derived compound may also exhibit LC phase characteristics only after mixing with other compounds and/or after polymerization. Typical liquid crystal origin is, for example, a hard rod or disk unit. Terms and definitions used in connection with liquid crystallinity or LC compounds are summarized in Pure Appl. Chem. 73 (5), 888 (2001) and C. Tschierske, G. Pelzl, S. Diele, Angew. Chem. 2004, 116, 6340. -6368.

術語"間隔基"(上下文中亦稱為"Sp")已為熟習此項技術者所知且描述於文獻中，參見例如Pure Appl.Chem.73(5),888(2001)及C.Tschierske,G.Pelzl,S.Diele,Angew.Chem.2004,116,6340－6368。除非另外指明，否則上下文中之術語"間隔基團"或"間隔基"表示可聚合液晶原性化合物("RM")中將液晶原性與可聚合基團彼此連接的柔性基團。The term "spacer" (also referred to as "Sp" in the context) is known to those skilled in the art and is described in the literature, see, for example, Pure Appl. Chem. 73 (5), 888 (2001) and C. Tschierske. , G. Pelzl, S. Diele, Angew. Chem. 2004, 116, 6340-6368. The term "spacer group" or "spacer" in this context, unless otherwise indicated, refers to a flexible group in a polymerizable liquid crystal-derived compound ("RM") that links liquid crystals to a polymerizable group to each other.

術語"反應性液晶原"或"RM"表示含有液晶原性及一或多個適用於聚合之官能基(亦稱可聚合基團或基團P)的化合物。The term "reactive mesogen" or "RM" denotes a compound containing liquid crystal origin and one or more functional groups (also known as polymerizable groups or groups P) suitable for polymerization. Things.

術語"低分子量化合物"及"不可聚合化合物"表示不含有在熟習此項技術者已知之一般條件下、尤其在用於RM聚合之條件下適於聚合之任何官能基的化合物，一般為單體。The terms "low molecular weight compound" and "non-polymerizable compound" mean a compound which does not contain any functional group suitable for polymerization under the general conditions known to those skilled in the art, especially under the conditions for RM polymerization, generally a monomer. .

術語"有機基團"表示碳或烴基團。The term "organic group" means a carbon or hydrocarbon group.

術語"碳基團"表示含有至少一個碳原子、不含其他原子的單價或多價有機基團(諸如－C≡C－)，或含有至少一個碳原子、視需要含有一或多個其他原子(諸如N、O、S、P、Si、Se、As、Te或Ge)的單價或多價有機基團(例如羰基等)。術語"烴基團"表示另外含有一或多個H原子及視需要一或多個雜原子(諸如N、O、S、P、Si、Se、As、Te或Ge)的碳基團。The term "carbon group" means a monovalent or polyvalent organic group (such as -C≡C-) containing at least one carbon atom, free of other atoms, or containing at least one carbon atom, optionally containing one or more other atoms. A monovalent or polyvalent organic group (such as carbonyl, etc.) such as N, O, S, P, Si, Se, As, Te or Ge. The term "hydrocarbon group" denotes a carbon group additionally containing one or more H atoms and optionally one or more heteroatoms such as N, O, S, P, Si, Se, As, Te or Ge.

"鹵素"表示F、Cl、Br或I。"Halogen" means F, Cl, Br or I.

碳基團或烴基團可為飽和或不飽和基團。不飽和基團為例如芳基、烯基或炔基。具有3個以上C原子的碳基團或烴基團可為直鏈、支鏈及/或環狀基團且亦可具有螺連接或稠環。The carbon group or hydrocarbon group can be a saturated or unsaturated group. The unsaturated group is, for example, an aryl group, an alkenyl group or an alkynyl group. A carbon group or a hydrocarbon group having 3 or more C atoms may be a linear, branched, and/or cyclic group and may have a spiro linkage or a fused ring.

術語"烷基"、"芳基"、"雜芳基"等亦涵蓋多價基團，例如伸烷基、伸芳基、伸雜芳基等。The terms "alkyl", "aryl", "heteroaryl" and the like also encompass polyvalent groups such as alkyl, aryl, heteroaryl and the like.

術語"芳基"表示芳族碳基團或由其衍生的基團。術語"雜芳基"表示含有一或多個雜原子之如上定義的"芳基"。The term "aryl" denotes an aromatic carbon group or a group derived therefrom. The term "heteroaryl" denotes an "aryl" group as defined above containing one or more heteroatoms.

較佳的碳基團及烴基團為具有1至40、較佳1至25、尤其較佳1至18個C原子之視需要經取代的烷基、烯基、炔基、烷氧基、烷基羰基、烷氧基羰基、烷基羰氧基及烷氧基羰氧基；具有6至40、較佳6至25個C原子之視需要經取代的芳基或芳氧基；或具有6至40個、較佳6至25個C原子之視需要經取代的烷基芳基、芳基烷基、烷基芳氧基、芳基烷氧基、芳基羰基、芳氧基羰基、芳基羰氧基及芳氧基羰氧基。Preferred carbon groups and hydrocarbon groups are optionally substituted alkyl, alkenyl, alkynyl groups having from 1 to 40, preferably from 1 to 25, particularly preferably from 1 to 18, C atoms. Alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy and alkoxycarbonyloxy; optionally substituted aryl or aryloxy having 6 to 40, preferably 6 to 25, C atoms Or an optionally substituted alkylaryl, arylalkyl, alkylaryloxy, arylalkoxy, arylcarbonyl, aryl having 6 to 40, preferably 6 to 25, C atoms Oxycarbonyl, arylcarbonyloxy and aryloxycarbonyloxy.

其他較佳的碳基團及烴基團為C₁ －C₄₀ 烷基、C₂ －C₄₀ 烯基、C₂ －C₄₀ 炔基、C₃ －C₄₀ 烯丙基、C₄ －C₄₀ 烷二烯基、C₄ －C₄₀ 多烯基、C₆ －C₄₀ 芳基、C₆ －C₄₀ 烷基芳基、C₆ －C₄₀ 芳基烷基、C₆ －C₄₀ 烷基芳氧基、C₆ －C₄₀ 芳基烷氧基、C₂ －C₄₀ 雜芳基、C₄ －C₄₀ 環烷基、C₄ －C₄₀ 環烯基等。尤其較佳為C₁ －C₂₂ 烷基、C₂ －C₂₂ 烯基、C₂ －C₂₂ 炔基、C₃ －C₂₂ 烯丙基、C₄ －C₂₂ 烷二烯基、C₆ －C₁₂ 芳基、C₆ －C₂₀ 芳基烷基及C₂ －C₂₀ 雜芳基。Other preferred carbon groups and hydrocarbon groups are C ₁ -C ₄₀ alkyl, C ₂ -C ₄₀ alkenyl, C ₂ -C ₄₀ alkynyl, C ₃ -C ₄₀ allyl, C ₄ -C ₄₀ alkane Dienyl, C ₄ -C ₄₀ polyalkenyl, C ₆ -C ₄₀ aryl, C ₆ -C ₄₀ alkylaryl, C ₆ -C ₄₀ arylalkyl, C ₆ -C ₄₀ alkylaryloxy A C ₆ -C ₄₀ arylalkoxy group, a C ₂ -C ₄₀ heteroaryl group, a C ₄ -C ₄₀ cycloalkyl group, a C ₄ -C ₄₀ cycloalkenyl group or the like. Particularly preferred is a C ₁ -C ₂₂ alkyl, C ₂ -C ₂₂ alkenyl, C ₂ -C ₂₂ alkynyl, C ₃ -C ₂₂ allyl group, C ₄ -C ₂₂ alkyldienyl group, C ₆ - C ₁₂ aryl, C ₆ -C ₂₀ arylalkyl and C ₂ -C ₂₀ heteroaryl.

其他較佳的碳基團及烴基團為具有1至40個、較佳1至25個C原子、未經取代或經F、Cl、Br、I或CN單取代或多取代的直鏈、支鏈或環狀烷基，且其中一或多個非相鄰CH₂ 基團可彼此獨立地以O及/或S原子彼此間不直接相連之方式各自經以下基團置換：－C(R^x )＝C(R^x )－、－C≡C－、－N(R^x )－、－O－、－S－、－CO－、－CO－O－、－O－CO－、－O－CO－O－。Other preferred carbon groups and hydrocarbon groups are straight chain branches having from 1 to 40, preferably from 1 to 25, C atoms, unsubstituted or mono- or polysubstituted by F, Cl, Br, I or CN. a chain or a cyclic alkyl group, and wherein one or more non-adjacent CH ₂ groups are each independently interrupted by a group in which O and/or S atoms are not directly related to each other: -C(R ^x )=C(R ^x )-, -C≡C-, -N(R ^x )-, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O- CO-O-.

R^x 較佳表示H、鹵素、具有1至25個C原子的直鏈、支鏈或環狀烷基鏈，此外，其中一或多個非相鄰C原子可經－O－、－S－、－CO－、－CO－O－、－O－CO－、－O－CO－O－置換，且其中一或多個H原子可經以下基團置換：氟、具有6至40個C原子之視需要經取代的芳基或芳氧基，或具有2至40個C原子之視需要經取代的雜芳基或雜芳氧基。R ^x preferably represents H, a halogen, a linear, branched or cyclic alkyl chain having 1 to 25 C atoms, and further, one or more of the non-adjacent C atoms may be via -O-, -S- , -CO-, -CO-O-, -O-CO-, -O-CO-O- substitution, and one or more of the H atoms may be replaced by a group of fluorine having 6 to 40 C atoms A substituted aryl or aryloxy group, or an optionally substituted heteroaryl or heteroaryloxy group having 2 to 40 C atoms is required.

較佳烷基為例如甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、2－甲基丁基、正戊基、第二戊基、環戊基、正己基、環己基、2－乙基己基、正庚基、環庚基、正辛基、環辛基、正壬基、正癸基、正十一烷基、正十二烷基、十二烷基、三氟甲基、全氟正丁基、2,2,2－三氟乙基、全氟辛基、全氟己基等。Preferred alkyl groups are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-butyl, 2-methylbutyl, n-pentyl, Dipentyl, cyclopentyl, n-hexyl, cyclohexyl, 2-ethylhexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, n-decyl, n-decyl, n-undecyl, N-dodecyl, dodecyl, trifluoromethyl, perfluoro-n-butyl, 2,2,2-trifluoroethyl, perfluorooctyl, perfluorohexyl, and the like.

較佳的烯基為例如乙烯基、丙烯基、丁烯基、戊烯基、環戊烯基、己烯基、環己烯基、庚烯基、環庚烯基、辛烯基、環辛烯基等。Preferred alkenyl groups are, for example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctyl Alkenyl and the like.

較佳的炔基為例如乙炔基、丙炔基、丁炔基、戊炔基、己炔基、辛炔基等。Preferred alkynyl groups are, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, octynyl and the like.

較佳烷氧基為例如甲氧基、乙氧基、2－甲氧基乙氧基、正丙氧基、異丙氧基、正丁氧基、異丁氧基、第二丁氧基、第三丁氧基、2－甲基丁氧基、正戊氧基、正己氧基、正庚氧基、正辛氧基、正壬氧基、正癸氧基、正十一烷氧基、正十二烷氧基等。Preferred alkoxy groups are, for example, methoxy, ethoxy, 2-methoxyethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, second butoxy, Third butoxy, 2-methylbutoxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-decyloxy, n-decyloxy, n-undecyloxy, N-dodecyloxy and the like.

較佳胺基為例如二甲基胺基、甲基胺基、甲基苯基胺基、苯基胺基等。Preferred amine groups are, for example, dimethylamino, methylamino, methylphenylamino, phenylamino and the like.

芳基及雜芳基可為單環或多環基團，亦即，其可具有一環(諸如苯基)或兩個或兩個以上環，該等環亦可稠合(諸如萘基)或共價連接(諸如聯苯)，或含有稠合環與連接環之組合。雜芳基含有一或多個較佳選自O、N、S及Se的雜原子。The aryl and heteroaryl groups may be monocyclic or polycyclic groups, that is, they may have one ring (such as a phenyl group) or two or more rings, which may also be fused (such as naphthyl) or Covalently linked (such as biphenyl) or a combination of a fused ring and a linking ring. The heteroaryl group contains one or more heteroatoms preferably selected from the group consisting of O, N, S and Se.

尤其較佳為具有6至25個C原子的單環、二環或三環芳基，及具有2至25個C原子的單環、二環或三環雜芳基，該等基團視需要含有稠環且視需要經取代。此外較佳為5員、6員或7員芳基及雜芳基，此外其中一或多個CH基團可以O原子及/或S原子彼此間不直接相連之方式經N、S或O置換。Particularly preferred are monocyclic, bicyclic or tricyclic aryl groups having 6 to 25 C atoms, and monocyclic, bicyclic or tricyclic heteroaryl groups having 2 to 25 C atoms, which are as needed Contains a fused ring and is optionally substituted. Further preferred are 5, 6 or 7 member aryl and heteroaryl groups, and further one or more of the CH groups may be replaced by N, S or O in such a manner that the O atoms and/or the S atoms are not directly connected to each other. .

較佳芳基為例如苯基、聯苯、聯三苯、[1,1'：3',1"]聯三苯－2'－基、萘基、蒽、聯萘、菲、芘、二氫芘、、苝、并四苯、并五苯、苯并芘、茀、茚、茚并茀、螺二茀等。Preferred aryl groups are, for example, phenyl, biphenyl, terphenyl, [1,1':3',1"]biphenyl-2'-yl, naphthyl, anthracene, binaphthyl, phenanthrene, anthracene, di Hydroquinone, , hydrazine, tetracene, pentacene, benzopyrene, anthracene, anthracene, anthracene, and snail.

較佳雜芳基為：例如，5員環，諸如吡咯、吡唑、咪唑、1,2,3－***、1,2,4－***、四唑、呋喃、噻吩、硒吩、噁唑、異噁唑、1,2－噻唑、1,3－噻唑、1,2,3－噁二唑、1,2,4－噁二唑、1,2,5－噁二唑、1,3,4－噁二唑、1,2,3－噻二唑、1,2,4－噻二唑、1,2,5－噻二唑、1,3,4－噻二唑；6員環，諸如吡啶、噠嗪、嘧啶、吡嗪、1,3,5－三嗪、1,2,4－三嗪、1,2,3－三嗪、1,2,4,5－四嗪、1,2,3,4－四嗪、1,2,3,5－四嗪；或稠合基團，諸如吲哚、異吲哚、吲嗪、吲唑、苯并咪唑、苯并***、嘌呤、萘并咪唑、菲并咪唑、吡啶并咪唑、吡嗪并咪唑、喹喏啉并咪唑、苯并噁唑、萘并噁唑、蒽并噁唑、菲并噁唑、異噁唑、苯并噻唑、苯并呋喃、異苯并呋喃、二苯并呋喃、喹啉、異喹啉、喋啶、苯并－5,6－喹啉、苯并－6,7－喹啉、苯并－7,8－喹啉、苯并異喹啉、吖啶、啡噻嗪、啡噁嗪、苯并噠嗪、苯并嘧啶、喹喏啉、啡嗪、啶、氮雜咔唑、苯并咔啉、啡啶、啡啉、噻吩并 [2,3b]噻吩、噻吩并[3,2b]噻吩、二噻吩并噻吩、異苯并噻吩、二苯并噻吩、苯并噻二唑并噻吩，或該等基團之組合。雜芳基亦可經烷基、烷氧基、硫烷基、氟、氟烷基或其他芳基或雜芳基基團取代。Preferred heteroaryl groups are, for example, 5-membered rings such as pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, tetrazole, furan, thiophene, selenophene, oxalic Oxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1, 3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole; 6 members Rings such as pyridine, pyridazine, pyrimidine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, 1,2,4,5-tetrazine , 1,2,3,4-tetrazine, 1,2,3,5-tetrazine; or a condensed group such as anthracene, isoindole, pyridazine, oxazole, benzimidazole, benzotriene Azole, anthracene, naphthimidazole, phenamimidazole, pyridoimidazole, pyrazinoimidazole, quinoxalinimidazole, benzoxazole, naphthoxazole, indoloxazole, phenanthroxazole, isoxazole , benzothiazole, benzofuran, isobenzofuran, dibenzofuran, quinoline, isoquinoline, acridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzene And-7,8-quinoline, benzoisoquinoline, acridine, phenothiazine, phenoxazine, benzo Pyridazine, benzopyrimidine, quinoxaline, phenazine, Pyridine, azacarbazole, benzoporphyrin, phenanthridine, phenanthroline, thieno[2,3b]thiophene, thieno[3,2b]thiophene, dithienothiophene, isobenzothiophene, dibenzothiophene , benzothiadiazolothiophene, or a combination of such groups. Heteroaryl groups can also be substituted with alkyl, alkoxy, sulfanyl, fluoro, fluoroalkyl or other aryl or heteroaryl groups.

(非芳族)脂環及雜環基團包括飽和環(亦即，僅含有單鍵的彼等環)與部分不飽和環(亦即，亦可含有多鍵的彼等環)。雜環含有一或多個較佳選自Si、O、N、S及Se的雜原子。(Non-aromatic) alicyclic and heterocyclic groups include saturated rings (i.e., their rings containing only a single bond) and partially unsaturated rings (i.e., those rings which may also contain multiple bonds). The heterocycle contains one or more heteroatoms preferably selected from the group consisting of Si, O, N, S and Se.

(非芳族)脂環及雜環基團可為單環(亦即，僅含一個環)(諸如環己烷)或多環(亦即，含有複數個環)(諸如十氫萘或二環辛烷)。尤其較佳為飽和基團。此外較佳為具有3至25個C原子、視需要含有稠環且視需要經取代的單環、二環或三環基團。此外較佳為5員、6員、7員或8員碳環基，此外，其中一或多個C原子可經Si置換且/或一或多個CH基團可經N置換且/或一或多個非相鄰CH₂ 基團可經－O－及/或－S－置換。The (non-aromatic) alicyclic and heterocyclic groups may be monocyclic (ie, containing only one ring) (such as cyclohexane) or polycyclic (ie, containing a plurality of rings) (such as decalin or two) Cyclooctane). Particularly preferred is a saturated group. Further preferred are monocyclic, bicyclic or tricyclic groups having 3 to 25 C atoms, optionally containing a fused ring and optionally substituted. Further preferred is a 5-membered, 6-membered, 7-membered or 8-membered carbocyclic group, in addition, wherein one or more C atoms may be replaced by Si and/or one or more CH groups may be replaced by N and/or Or a plurality of non-adjacent CH ₂ groups may be replaced by -O- and/or -S-.

較佳的脂環及雜環基團為：例如，5員基團，諸如環戊烷、四氫呋喃、四氫硫呋喃、吡咯啶；6員基團，諸如環己烷、矽烷、環己烯、四氫哌喃、四氫硫哌喃、1,3－二噁烷、1,3－二噻烷、哌啶；7員基團，諸如環庚烷；及稠合基團，諸如四氫萘、十氫萘、茚滿、二環[1.1.1]戊烷－1,3－二基、二環[2.2.2]辛烷－1,4－二基、螺[3.3]庚烷－2,6－二基、八氫－4,7－甲橋茚滿－2,5－二基。Preferred alicyclic and heterocyclic groups are, for example, a 5-member group such as cyclopentane, tetrahydrofuran, tetrahydrofuran, pyrrolidine; a 6-member group such as cyclohexane, decane, cyclohexene, Tetrahydropyran, tetrahydrothiopyran, 1,3-dioxane, 1,3-dithiane, piperidine; a 7-member group such as cycloheptane; and a condensed group such as tetrahydronaphthalene , decahydronaphthalene, indane, bicyclo[1.1.1]pentane-1,3-diyl, bicyclo[2.2.2]octane-1,4-diyl, spiro[3.3]heptane-2 , 6-diyl, octahydro-4,7-methyl bridge indole-2,5-diyl.

芳基、雜芳基、碳基團及烴基團視需要具有一或多個較佳選自由以下各基組成之群的取代基：矽烷基、磺基、磺醯基、甲醯基、胺、亞胺、腈、巰基、硝基、鹵素、C_1－12 烷基、C_6－12 芳基、C_1－12 烷氧基、羥基，或該等基團之組合。The aryl, heteroaryl, carbon group and hydrocarbon group optionally have one or more substituents selected from the group consisting of alkyl, sulfo, sulfonyl, decyl, amine, Imine, nitrile, fluorenyl, nitro, halogen, C _1-12 alkyl, C _6-12 aryl, C _1-12 alkoxy, hydroxy, or a combination of such groups.

較佳取代基為例如溶解促進性基團，諸如烷基或烷氧基；吸電子基團，諸如氟、硝基或腈；或使聚合物之玻璃轉移溫度(Tg)增大的取代基，尤其巨大基團，諸如第三丁基或視需要經取代之芳基。Preferred substituents are, for example, a dissolution-promoting group such as an alkyl group or an alkoxy group; an electron withdrawing group such as fluorine, a nitro group or a nitrile; or a substituent which increases the glass transition temperature (Tg) of the polymer, Especially large groups such as tert-butyl or optionally substituted aryl groups.

較佳取代基(下文亦稱為"L")為例如OH、CH₂ OH、F、Cl、Br、I、－CN、－NO₂ 、－NCO、－NCS、－OCN、－SCN、－C(＝O)N(R^x )₂ 、－C(＝O)Y¹ 、－C(＝O)R^x 、－N(R^x )₂ ，其中R^x 具有上述含義，且Y¹ 表示鹵素、具有6至40個、較佳6至20個C原子之視需要經取代的矽烷基或芳基，及具有1至25個C原子的直鏈或支鏈烷基、烷氧基、烷基羰基、烷氧基羰基、烷基羰氧基或烷氧基羰氧基，其中一或多個H原子視需要可經F或Cl置換。Preferred substituents (hereinafter also referred to as "L") are, for example, OH, CH ₂ OH, F, Cl, Br, I, -CN, -NO ₂ , -NCO, -NCS, -OCN, -SCN, -C (=O)N(R ^x ) ₂ , -C(=O)Y ¹ , -C(=O)R ^x , -N(R ^x ) ₂ , wherein R ^x has the above meaning, and Y ¹ represents halogen, An optionally substituted decyl or aryl group having 6 to 40, preferably 6 to 20 C atoms, and a linear or branched alkyl group having 1 to 25 C atoms, an alkoxy group, an alkylcarbonyl group An alkoxycarbonyl group, an alkylcarbonyloxy group or an alkoxycarbonyloxy group, wherein one or more H atoms may be substituted by F or Cl as needed.

"經取代之矽烷基或芳基"較佳意謂經以下各基取代之矽烷基或芳基：鹵素、－CN、R⁰ 、－OR⁰ 、－CO－R⁰ 、－CO－O－R⁰ 、－O－CO－R⁰ 或－O－CO－O－R⁰ ，其中R⁰ 具有上述含義。"Substituted alkyl or aryl" preferably means a decyl or aryl group substituted by the following groups: halogen, -CN, R ⁰ , -OR ⁰ , -CO-R ⁰ , -CO-O-R ⁰ , -O-CO-R ⁰ or -O-CO-O-R ⁰ , wherein R ⁰ has the above meaning.

尤其較佳的取代基L為例如F、Cl、CN、NO₂ 、CH₃ 、C₂ H₅ 、OCH₃ 、OC₂ H₅ 、COCH₃ 、COC₂ H₅ 、COOCH₃ 、COOC₂ H₅ 、CF₃ 、OCF₃ 、OCHF₂ 、OC₂ F₅ ，此外為苯基。Particularly preferred substituents L are, for example, F, Cl, CN, NO ₂ , CH ₃ , C ₂ H ₅ , OCH ₃ , OC ₂ H ₅ , COCH ₃ , COC ₂ H ₅ , COOCH ₃ , COOC ₂ H ₅ , CF ₃ , OCF ₃ , OCHF ₂ , OC ₂ F ₅ , in addition to phenyl.

較佳為或其中L具有上述含義之一。 Preferred or Where L has one of the above meanings.

可聚合基團P、P^a 或P^b 為適用於聚合反應(諸如自由基或離子鏈聚合、加聚或縮聚反應)或適用於聚合物類似反應(例如加成或縮合於聚合物主鏈上)的基團。尤其較佳為用於鏈聚合的基團(尤其含有C＝C雙鍵或C≡C參鍵的彼等基團)及適用於開環聚合的基團，諸如氧雜環丁烷或環氧化物基團。The polymerizable group P, P ^a or P ^b is suitable for polymerization (such as radical or ionic chain polymerization, polyaddition or polycondensation) or for polymer-like reactions (for example addition or condensation on the polymer backbone) ) of the group. Particularly preferred are groups for chain polymerization (especially those having a C=C double bond or a C≡C bond) and groups suitable for ring opening polymerization, such as oxetane or epoxy. Compound group.

較佳的可聚合基團選自：CH₂ ＝CW¹ －COO－、CH₂ ＝CW¹ －CO－、、、、CH₂ ＝CW² －(O)_k3 －、CW¹ ＝CH－CO－(O)_k3 －、CW¹ ＝CH－CO－NH－、CH₂ ＝CW¹ －CO－NH－、CH₃ －CH＝CH－O－、(CH₂ ＝CH)₂ CH－OCO－、(CH₂ ＝CH－CH₂ )₂ CH－OCO－、(CH₂ ＝CH)₂ CH－O－、(CH₂ ＝CH－CH₂ )₂ N－、(CH₂ ＝CH－CH₂ )₂ N－CO－、HO－CW² W³ －、HS－CW² W³ －、HW² N－、HO－CW² W³ －NH－、CH₂ ＝CW¹ －CO－NH－、CH₂ ＝CH－(COO)_k1 －Phe－(O)_k2 －、CH₂ ＝CH－(CO)_k1 －Phe－(O)_k2 －、Phe－CH＝CH－、HOOC－、OCN－及W⁴ W⁵ W⁶ Si－，其中W¹ 表示H、F、Cl、CN、CF₃ 、苯基或具有1至5個C原子之烷基，尤其H、F、Cl或CH₃ ，W² 及W³ 彼此獨立地各自表示H或具有1至5個C原子之烷基，尤其H、甲基、乙基或正丙基，W⁴ 、W⁵ 及W⁶ 彼此獨立地各自表示Cl、具有1至5個C原子之氧雜烷基或氧雜羰基烷基，W⁷ 及W⁸ 彼此獨立地各自表示H、Cl或具有1至5個C原子之烷基，Phe表示視需要經一或多個如上定義之基團L取代的1,4－伸苯基，且k₁ 、k₂ 及k₃ 彼此獨立地各自表示0或1，k₃ 較佳表示1。Preferred polymerizable groups are selected from the group consisting of CH ₂ =CW ¹ -COO-, CH ₂ =CW ¹ -CO-, , , , CH ₂ =CW ² -(O) _k3 -, CW ¹ =CH-CO-(O) _k3 -, CW ¹ =CH-CO-NH-, CH ₂ =CW ¹ -CO-NH-,CH ₃ - CH=CH-O-, (CH ₂ =CH) ₂ CH-OCO-, (CH ₂ =CH-CH ₂ ) ₂ CH-OCO-, (CH ₂ =CH) ₂ CH-O-, (CH ₂ = CH-CH ₂ ) ₂ N-, (CH ₂ =CH-CH ₂ ) ₂ N-CO-, HO-CW ² W ³ -, HS-CW ² W ³ -, HW ² N-, HO-CW ² W ³ -NH-, CH ₂ =CW ¹ -CO-NH-,CH ₂ =CH-(COO) _k1 -Phe-(O) _k2 -,CH ₂ =CH-(CO) _k1 -Phe-(O) _k2 -, Phe-CH=CH-, HOOC-, OCN- and W ⁴ W ⁵ W ⁶ Si-, wherein W ¹ represents H, F, Cl, CN, CF ₃ , phenyl or has 1 to 5 C atoms Alkyl groups, especially H, F, Cl or CH ₃ , W ² and W ³ each independently represent H or an alkyl group having 1 to 5 C atoms, especially H, methyl, ethyl or n-propyl, W ⁴ , W ⁵ and W ⁶ each independently represent Cl, an oxaalkyl group having 1 to 5 C atoms or an oxacarbonylalkyl group, and W ⁷ and W ⁸ each independently represent H, Cl or have 1 to 5 C atoms of alkyl, Phe means one or more as above The defined group L is substituted with 1,4-phenylene, and k ₁ , k ₂ and k ₃ each independently represent 0 or 1, and k ₃ preferably represents 1.

尤其較佳的可聚合基團為CH₂ ＝CH－COO－、CH₂ ＝C(CH₃ )－COO－、CH₂ ＝CH－、CH₂ ＝CH－O－、(CH₂ ＝CH)₂ CH－OCO－、(CH₂ ＝CH)₂ CH－O－、及，尤其乙烯氧基、丙烯酸酯、甲基丙烯酸酯、氟化丙烯酸酯、氯化丙烯酸酯、氧雜環丁烷及環氧化物。Particularly preferred polymerizable groups are CH ₂ =CH-COO-, CH ₂ =C(CH ₃ )-COO-, CH ₂ =CH-, CH ₂ =CH-O-, (CH ₂ =CH) ₂ CH-OCO-, (CH ₂ =CH) ₂ CH-O-, and In particular, ethyleneoxy, acrylate, methacrylate, fluorinated acrylate, chlorinated acrylate, oxetane and epoxide.

較佳間隔基Sp係選自式Sp'－X'，從而基團"P^(a,b) －Sp－"對應於式"P^(a,b) －Sp'－X'－"，其中Sp'表示具有1至20個、較佳1至12個C原子的伸烷基，其視需要經F、Cl、Br、I或CN單取代或多取代，且此外，其中一或多個非相鄰CH₂ 基團可彼此獨立地以O及/或S原子彼此間不直接相連之方式各自經以下基團置換：－O－、－S－、－NH－、－NR⁰ －、－SiR⁰ R⁰⁰ －、－CO－、－COO－、－OCO－、－OCO－O－、－S－CO－、－CO－S－、－NR⁰ －CO－O－、－O－CO－NR⁰ －、－NR⁰ －CO－NR⁰ －、－CH＝CH－或－C≡C－；X'表示－O－、－S－、－CO－、－COO－、－OCO－、－O－COO－、－CO－NR⁰ －、－NR⁰ －CO－、－NR⁰ －CO－NR⁰ －、－OCH₂ －、－CH₂ O－、－SCH₂ －、－CH₂ S－、－CF₂ O－、－OCF₂ －、－CF₂ S－、－SCF₂ －、－CF₂ CH₂ －、－CH₂ CF₂ －、－CF₂ CF₂ －、－CH＝N－、－N＝CH－、－N＝N－、－CH＝CR⁰ －、－CY² ＝CY³ －、－C≡C－、－CH＝CH－COO－、－OCO－CH＝CH－或單鍵；R⁰ 及R⁰⁰ 彼此獨立地各自表示H或具有1至12個C原子的烷基；且Y² 及Y³ 彼此獨立地各自表示H、F、Cl或CN。Preferably, the spacer Sp is selected from the group of Sp'-X' such that the group "P ^(a,b) -Sp-" corresponds to the formula "P ^(a,b) -Sp'-X'-", wherein Sp 'Expressed to an alkylene group having 1 to 20, preferably 1 to 12, C atoms, which may be mono- or polysubstituted by F, Cl, Br, I or CN, and furthermore, one or more of the non-phases The ortho CH ₂ groups may be independently substituted with each other such that O and/or S atoms are not directly bonded to each other by the following groups: -O-, -S-, -NH-, -NR ⁰ -, -SiR ⁰ R ⁰⁰ -, -CO-, -COO-, -OCO-, -OCO-O-, -S-CO-, -CO-S-, -NR ⁰ -CO-O-, -O-CO-NR ⁰ -, -NR ⁰ -CO-NR ⁰ -, -CH=CH- or -C≡C-; X' represents -O-, -S-, -CO-, -COO-, -OCO-, -O- COO-, -CO-NR ⁰ -, -NR ⁰ -CO-, -NR ⁰ -CO-NR ⁰ -, -OCH ₂ -, -CH ₂ O-, -SCH ₂ -, -CH ₂ S-, - CF ₂ O-, -OCF ₂ -, -CF ₂ S-, -SCF ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -CF ₂ CF ₂ -, -CH=N-, -N =CH-, -N=N-, -CH=CR ⁰ -, -CY ² =CY ³ -, -C≡C-, -CH=CH-COO-, -OCO-CH=CH- or a single bond; R ⁰ and R ⁰⁰ are each independently represented H or an alkyl group having 1 to 12 C atoms; and Y ² and Y ³ each independently represent H, F, Cl or CN.

X'較佳為－O－、－S－、－CO－、－COO－、－OCO－、－O－COO－、－CO－NR⁰ －、－NR⁰ －CO－、－NR⁰ －CO－NR⁰ －或單鍵。X' is preferably -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR ⁰ -, -NR ⁰ -CO-, -NR ⁰ -CO -NR ⁰ - or single button.

典型間隔基Sp'為例如－(CH₂ )_p1 －、－(CH₂ CH₂ O)_q1 －CH₂ CH₂ －、－CH₂ CH₂ －S－CH₂ CH₂ －、－CH₂ CH₂ －NH－CH₂ CH₂ －或－(SiR⁰ R⁰⁰ －O)_p1 －，其中p1為1至12之整數，q1為1至3之整數，且R⁰ 及R⁰⁰ 具有上述含義。Typical spacer groups Sp ', for example, _{_{- (CH 2) p1 -,}} - (CH 2 CH 2 O) q1 -CH 2 CH 2 -, - CH 2 CH 2 -S-CH 2 CH 2 -, - CH 2 CH 2 -NH-CH ₂ CH ₂ - or -(SiR ⁰ R ⁰⁰ -O) _p1 -, wherein p1 is an integer from 1 to 12, q1 is an integer from 1 to 3, and R ⁰ and R ⁰⁰ have the above meanings.

尤其較佳的基團－X'－Sp'－為－(CH₂ )_p1 －、－O－(CH₂ )_p1 －、－OCO－(CH₂ )_p1 －、－OCOO－(CH₂ )_p1 －。Particularly preferred groups -X'-Sp'- are -(CH ₂ ) _p1 -, -O-(CH ₂ ) _p1 -, -OCO-(CH ₂ ) _p1 -, -OCOO-(CH ₂ ) _p1 -.

尤其較佳的基團Sp'為例如各種情況下之直鏈伸乙基、伸丙基、伸丁基、伸戊基、伸已基、伸庚基、伸辛基、伸壬基、伸癸基、伸十一烷基、伸十二烷基、伸十八烷基、伸乙氧基伸乙基、亞甲氧基伸丁基、伸乙硫基伸乙基、伸乙基－N－甲基亞胺基伸乙基、1－甲基伸烷基、伸乙烯基、伸丙烯基及伸丁烯基。Particularly preferred groups Sp' are, for example, a straight chain extended ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an exopeptide group, a hydrazine group, and a hydrazine group. Base, undecydecyl, dodecyl, octadecyl, ethoxylated ethyl, methyleneoxybutyl, ethyl thioethyl, ethyl ethyl-N-methyl The amine group is an ethyl group, a 1-methylalkyl group, a vinyl group, a propylene group and a butenyl group.

可聚合化合物以類似於熟習此項技術者已知且描述於有機化學之標準著作中的方法製備，諸如Houben－Weyl,Methoden der organischen Chemie[Methods of Organic Chemistry],Thieme－Verlag,Stuttgart。式I之可聚合丙烯酸酯及甲基丙烯酸酯可類似於US 5,723,066中所述的方法進行合成。此外，實例中提供尤其較佳的方法。Polymerizable compounds are prepared in a manner similar to that known to those skilled in the art and described in standard work of organic chemistry, such as Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Thieme-Verlag, Stuttgart. The polymerizable acrylates and methacrylates of formula I can be synthesized analogously to the methods described in US 5,723,066. Moreover, a particularly preferred method is provided in the examples.

在最簡單的情況下，可藉由在脫水試劑(諸如DCC(二環己基碳化二醯亞胺))存在下、使用含有基團P之相應酸、酸衍生物或鹵代化合物(諸如(甲基)丙烯醯氯或(甲基)丙烯酸)將可市購之通式HO－A¹ －(Z¹ －A² )_m －OH之二醇，諸如2,6－二羥基萘(萘－2,6－二醇)或1－(4－羥基苯基)苯基－4－醇進行酯化或醚化來進行合成，其中A¹ 、A² 、Z¹ 及m具有上述含義。In the simplest case, by using a corresponding acid, acid derivative or halogenated compound containing a group P in the presence of a dehydrating reagent such as DCC (dicyclohexylcarbodiimide) (such as (A) Acryl chloride or (meth)acrylic acid. A diol of the general formula HO-A ¹ -(Z ¹ -A ² ) _m -OH, such as 2,6-dihydroxynaphthalene (naphthalene-2) Synthesis of 6-diol) or 1-(4-hydroxyphenyl)phenyl-4-ol by esterification or etherification, wherein A ¹ , A ² , Z ¹ and m have the above meanings.

可聚合化合物係藉由在施加電壓下、在LC顯示器之基板之間的LC介質中進行就地聚合反應來聚合或交聯(若化合物含有兩個或兩個以上的可聚合基團)。適當且較佳的聚合方法為例如熱聚合或光聚合法，較佳光聚合法，尤其UV光聚合法。必要時，亦可將一或多種引發劑添加於其中。聚合反應的適當條件及引發劑之適當類型及量已為熟習此項技術者所知且已描述於文獻中。適用於自由基聚合反應的引發劑為例如可市購的光引發劑Irgacure65l、Irgacure184、Irgacure907、Irgacure369或Darocure1173(Ciba AG)。若使用引發劑，則其在整個混合物中的比例較佳為0.001至5 wt%，尤其較佳0.001至1 wt%。然而，聚合反應亦可在不添加引發劑的情況下進行。在另一較佳實施例中，LC介質不包含聚合引發劑。The polymerizable compound is polymerized or crosslinked by in situ polymerization under an applied voltage in an LC medium between substrates of the LC display (if the compound contains two or more polymerizable groups). Suitable and preferred polymerization methods are, for example, thermal polymerization or photopolymerization, preferably photopolymerization, especially UV photopolymerization. One or more initiators may also be added thereto as necessary. Suitable conditions for the polymerization and the appropriate type and amount of initiator are known to those skilled in the art and have been described in the literature. Suitable initiators for free radical polymerization are, for example, commercially available photoinitiators Irgacure 65l. Irgacure184 Irgacure907 Irgacure369 Or Darocure1173 (Ciba AG). If an initiator is used, its proportion in the entire mixture is preferably from 0.001 to 5 wt%, particularly preferably from 0.001 to 1 wt%. However, the polymerization can also be carried out without adding an initiator. In another preferred embodiment, the LC medium does not comprise a polymerization initiator.

可聚合組分A)或LC介質亦可包含一或多種穩定劑，以防止非所要之RM自發聚合(例如在儲存或運輸期間)。穩定劑的適當類型及量已為熟習此項技術者所知且描述於文獻中。尤其適當為例如可市購的Irganox系列穩定劑(Ciba AG)。若使用穩定劑，則其比例，以RM或可聚合組分A)之總量計，較佳為10－5000 ppm，尤其較佳50－500 ppm。The polymerizable component A) or the LC medium may also contain one or more stabilizers to prevent undesired spontaneous polymerization of the RM (eg, during storage or transportation). Suitable types and amounts of stabilizers are known to those skilled in the art and are described in the literature. Particularly suitable for example is commercially available Irganox Series stabilizers (Ciba AG). If a stabilizer is used, the proportion thereof is preferably from 10 to 5,000 ppm, particularly preferably from 50 to 500 ppm, based on the total of RM or the polymerizable component A).

本發明之可聚合化合物尤其適於無引發劑情況下的聚合，此具有很大優勢，諸如材料成本更低且尤其可能殘餘量之引發劑或其降解產物對LC介質的污染更小。The polymerizable compounds of the invention are especially suitable for polymerization in the absence of initiators, which have great advantages, such as lower material costs and, in particular, possible residual amounts of initiators or their degradation products which have less contamination of the LC medium.

本發明之LC介質較佳包含<5%、尤其較佳<1%、極其較佳<0.5%的可聚合化合物，尤其上述式之可聚合化合物。The LC medium of the present invention preferably comprises <5%, particularly preferably <1%, and most preferably <0.5% of a polymerizable compound, especially a polymerizable compound of the above formula.

本發明之可聚合化合物可單獨添加至LC介質中，但亦可使用包含兩種或兩種以上本發明之可聚合化合物的混合物或包含一或多種本發明之可聚合化合物及一或多種其他可聚合化合物(共聚單體)的混合物。共聚單體可為液晶原性或非液晶原性。將此類混合物聚合時，形成共聚物。本發明此外係關於上文及下文所述的可聚合混合物。The polymerizable compound of the present invention may be added to the LC medium alone, but a mixture comprising two or more of the polymerizable compounds of the present invention or one or more polymerizable compounds of the present invention and one or more other may be used. A mixture of polymeric compounds (comonomers). The comonomer can be liquid crystalline or non-liquid crystalline. When such a mixture is polymerized, a copolymer is formed. The invention further relates to the polymerizable mixtures described above and below.

適當且較佳的液晶原性共聚單體為例如選自以下式的彼等物：其中：P¹ 及P² 具有針對P所指明之含義之一且較佳表示丙烯酸酯或甲基丙烯酸酯；Sp¹ 及Sp² 具有針對Sp所指明之含義之一或表示單鍵；Z² 及Z³ 彼此獨立地各自表示－COO－或－OCO－； L表示P－Sp－、F、Cl、Br、I、－CN、－NO₂ 、－NCO、－NCS、－OCN、－SCN、－C(＝O)N(R^x )₂ 、－C(＝O)Y¹ 、－C(＝O)R^x 、－N(R^x )₂ 、視需要經取代之矽烷基、具有6至20個C原子之視需要經取代之芳基，或具有1至25個C原子之直鏈或支鏈烷基、烷氧基、烷基羰基、烷氧基羰基、烷基羰氧基或烷氧基羰氧基，此外，其中一或多個H原子可經F、Cl或P－Sp－置換；L'及L"彼此獨立地各自表示H、F或Cl；r表示0、1、2、3或4；s表示0、1、2或3；t表示0、1或2；x表示0或1，且R^y 及R^z 彼此獨立地各自表示H或CH₃ 。Suitable and preferred liquid crystalline comonomers are, for example, those selected from the group consisting of: Wherein: P ¹ and P ² have one of the meanings indicated for P and preferably represent acrylate or methacrylate; and Sp ¹ and Sp ² have one of the meanings indicated for Sp or represent a single bond; Z ² and Z ³ each independently represents -COO- or -OCO-; L represents P-Sp-, F, Cl, Br, I, -CN, -NO ₂ , -NCO, -NCS, -OCN, -SCN, - C(=O)N(R ^x ) ₂ , -C(=O)Y ¹ , -C(=O)R ^x , -N(R ^x ) ₂ , optionally substituted alkylene group, having 6 to 20 a C atom to be substituted with an aryl group, or a linear or branched alkyl group having 1 to 25 C atoms, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkoxy group a carbonyloxy group, furthermore, wherein one or more H atoms may be substituted by F, Cl or P-Sp-; L' and L" each independently represent H, F or Cl; r represents 0, 1, 2 3 or 4; s represents 0, 1, 2 or 3; t represents 0, 1 or 2; x represents 0 or 1, and R ^y and R ^z each independently represent H or CH ₃ .

除上述可聚合化合物之外，用於本發明之LC顯示器的LC介質包含含有一或多種、較佳兩種或兩種以上之低分子量(亦即單體或非聚合)化合物的LC混合物("主體混合物")。該等低分子量化合物在可聚合化合物之聚合反應所用的條件下穩定或對聚合反應不反應。原則上，適用於習知VA及OCB顯示器的任何LC混合物適用作主體混合物。適當的LC混合物已為熟習此項技術者所知且描述於文獻中，例如，VA顯示器之混合物描述於EP 1 378 557 A1中且OCB顯示器之混合物描述於EP 1 306 418 A1及DE 102 24 046 A1中。In addition to the above polymerizable compounds, the LC medium used in the LC display of the present invention comprises an LC mixture containing one or more, preferably two or more, low molecular weight (i.e., monomeric or non-polymeric) compounds (" Host mixture "). These low molecular weight compounds are stable under the conditions used for the polymerization of the polymerizable compound or do not react with the polymerization reaction. In principle, any LC mixture suitable for use in conventional VA and OCB displays is suitable as the host mixture. Suitable LC mixtures are known to the person skilled in the art and are described in the literature. For example, mixtures of VA displays are described in EP 1 378 557 A1 and mixtures of OCB displays are described in EP 1 306 418 A1 and DE 102 24 046 In A1.

尤其較佳的主體混合物及LC介質指明如下：Particularly preferred host mixtures and LC media are indicated below:

a)包含一或多種選自以下式之化合物的LC介質： a) an LC medium comprising one or more compounds selected from the group consisting of:

其中個別基團具有以下含義：a表示1或2；b表示0或1；表示或R¹ 及R² 彼此獨立地各自表示具有1至12個C原子的烷基，此外，其中一或兩個非相鄰CH₂ 基團可以O原子彼此間不直接相連之方式經－O－、－CH＝CH－、－CO－、－OCO－或－COO－置換，較佳表示具有1至6個C原子的烷基或烷氧基；Z^x 及Z^y 彼此獨立地各自表示－CH₂ CH₂ －、－CH＝CH－、－CF₂ O－、－OCF₂ －、－CH₂ O－、－OCH₂ －、－COO－、－OCO－、－C₂ F₄ －、－CF＝CF－、－CH＝CHCH₂ O－或單鍵，較佳表示單鍵； L^1－4 彼此獨立地各自表示F、Cl、OCF₃ 、CF₃ 、CH₃ 、CH₂ F、CHF₂ 。Wherein individual groups have the following meanings: a represents 1 or 2; b represents 0 or 1; Express or R ¹ and R ² each independently represent an alkyl group having 1 to 12 C atoms, and further, one or two non-adjacent CH ₂ groups may be O-, in such a manner that O atoms are not directly connected to each other. -CH=CH-, -CO-, -OCO- or -COO-substitution, preferably denotes an alkyl or alkoxy group having 1 to 6 C atoms; Z ^x and Z ^y each independently represent -CH ₂ CH ₂ -, -CH=CH-, -CF ₂ O-, -OCF ₂ -, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -C ₂ F ₄ -, -CF= CF-, -CH=CHCH ₂ O- or a single bond, preferably represents a single bond; L ^1-4 each independently represents F, Cl, OCF ₃ , CF ₃ , CH ₃ , CH ₂ F, CHF ₂ .

較佳地，基團L¹ 與L² 表示F，或基團L¹ 與L² 中之一者表示F且另一者表示Cl，或基團L³ 與L⁴ 皆表示F，或基團L³ 與L⁴ 中之一者表示F且另一者表示Cl。Preferably, the groups L ¹ and L ² represent F, or one of the groups L ¹ and L ² represents F and the other represents Cl, or the groups L ³ and L ^{4 both} represent F, or a group One of L ³ and L ⁴ represents F and the other represents Cl.

式CY之化合物較佳選自以下子式：其中a表示1或2，烷基及烷基^＊彼此獨立地各自表示具有1－6個C原子的直鏈烷基，且烯基表示具有2－6個C原子的直鏈烯基。烯基較佳表示CH₂ ＝CH－、CH₂ ＝CHCH₂ CH₂ －、CH₃ －CH＝CH－、CH₃ －CH₂ －CH＝CH－、CH₃ －(CH₂ )₂ －CH＝CH－、CH₃ －(CH₂ )₃ －CH＝CH－或CH₃ －CH＝CH－(CH₂ )₂ －。The compound of formula CY is preferably selected from the following subtypes: Wherein a represents 1 or 2, and the alkyl group and the alkyl group ^* each independently represent a linear alkyl group having 1 to 6 C atoms, and the alkenyl group means a linear alkenyl group having 2 to 6 C atoms. The alkenyl group preferably represents CH ₂ =CH-, CH ₂ =CHCH ₂ CH ₂ -, CH ₃ -CH=CH-, CH ₃ -CH ₂ -CH=CH-, CH ₃ -(CH ₂ ) ₂ -CH= CH-, CH ₃ -(CH ₂ ) ₃ -CH=CH- or CH ₃ -CH=CH-(CH ₂ ) ₂ -.

式PY之化合物較佳選自以下子式：其中烷基及烷基^＊彼此獨立地各自表示具有1－6個C原子的直鏈烷基，且烯基表示具有2－6個C原子的直鏈烯基。烯基較佳表示CH₂ ＝CH－、CH₂ ＝CHCH₂ CH₂ －、CH₃ －CH＝CH－、CH₃ －CH₂ －CH＝CH－、CH₃ －(CH₂ )₂ －CH＝CH－、CH₃ －(CH₂ )₃ －CH＝CH－或CH₃ －CH＝CH－(CH₂ )₂ －。The compound of formula PY is preferably selected from the following subtypes: Wherein the alkyl group and the alkyl group ^* each independently represent a linear alkyl group having 1 to 6 C atoms, and the alkenyl group means a linear alkenyl group having 2 to 6 C atoms. The alkenyl group preferably represents CH ₂ =CH-, CH ₂ =CHCH ₂ CH ₂ -, CH ₃ -CH=CH-, CH ₃ -CH ₂ -CH=CH-, CH ₃ -(CH ₂ ) ₂ -CH= CH-, CH ₃ -(CH ₂ ) ₃ -CH=CH- or CH ₃ -CH=CH-(CH ₂ ) ₂ -.

b)另外包含一或多種下式之化合物的LC介質： b) an LC medium additionally comprising one or more compounds of the formula:

其中個別基團具有以下含義：表示或表示或R³ 及R⁴ 彼此獨立地各自表示具有1至12個C原子的烷基，此外，其中一或兩個非相鄰CH₂ 基團可以O原子彼此間不直接相連之方式經－O－、－CH＝CH－、－CO－、－OCO－或－COO－置換；Z^y 表示－CH₂ CH₂ －、－CH＝CH－、－CF₂ O－、－OCF₂ －、－CH₂ O－、－OCH₂ －、－COO－、－OCO－、－C₂ F₄ －、－CF＝CF－、－CH＝CHCH₂ O－或單鍵，較佳表示單鍵。Some of these groups have the following meanings: Express or Express or R ³ and R ⁴ each independently represent an alkyl group having 1 to 12 C atoms, and further, one or two non-adjacent CH ₂ groups may be via O-, in a manner in which O atoms are not directly connected to each other. -CH=CH-, -CO-, -OCO- or -COO-substitution; Z ^y represents -CH ₂ CH ₂ -, -CH=CH-, -CF ₂ O-, -OCF ₂ -, -CH ₂ O -, -OCH ₂ -, -COO-, -OCO-, -C ₂ F ₄ -, -CF=CF-, -CH=CHCH ₂ O- or a single bond, preferably a single bond.

式ZK之化合物較佳選自以下子式：其中烷基及烷基^＊彼此獨立地各自表示具有1－6個C原子的直鏈烷基，且烯基表示具有2－6個C原子的直鏈烯基。烯基較佳表示CH₂ ＝CH－、CH₂ ＝CHCH₂ CH₂ －、CH₃ －CH＝CH－、CH₃ －CH₂ －CH＝CH－、CH₃ －(CH₂ )₂ －CH＝CH－、CH₃ －(CH₂ )₃ －CH＝CH－或CH₃ －CH＝CH－(CH₂ )₂ －。The compound of formula ZK is preferably selected from the following subtypes: Wherein the alkyl group and the alkyl group ^* each independently represent a linear alkyl group having 1 to 6 C atoms, and the alkenyl group means a linear alkenyl group having 2 to 6 C atoms. The alkenyl group preferably represents CH ₂ =CH-, CH ₂ =CHCH ₂ CH ₂ -, CH ₃ -CH=CH-, CH ₃ -CH ₂ -CH=CH-, CH ₃ -(CH ₂ ) ₂ -CH= CH-, CH ₃ -(CH ₂ ) ₃ -CH=CH- or CH ₃ -CH=CH-(CH ₂ ) ₂ -.

c)另外包含一或多種下式之化合物的LC介質： c) an LC medium additionally comprising one or more compounds of the formula:

其中個別基團在各自出現時相同或不同地具有以下含義：R⁵ 及R⁶ 彼此獨立地各自具有如上針對R¹ 所指明之含義之一，表示或表示或及e表示1或2。Wherein the individual groups have the same or different meanings when they occur, respectively: R ⁵ and R ⁶ independently of one another each have ^one of the meanings indicated above for R ¹ , Express or Express or And e means 1 or 2.

式DK之化合物較佳選自以下子式： The compound of formula DK is preferably selected from the following subtypes:

其中烷基及烷基^＊彼此獨立地各自表示具有1－6個C原子的直鏈烷基，且烯基及烯基^＊彼此獨立地各自表示具有2－6個C原子的直鏈烯基。烯基及烯基^＊較佳表示CH₂ ＝CH－、CH₂ ＝CHCH₂ CH₂ －、CH₃ －CH＝CH－、CH₃ －CH₂ －CH＝CH－、CH₃ －(CH₂ )₂ －CH＝CH－、CH₃ －(CH₂ )₃ －CH＝CH－或CH₃ －CH＝CH－(CH₂ )₂ －。Wherein the alkyl and alkyl ^* each, independently represents a linear alkyl group having 1-6 C atoms, and alkenyl and alkenyl ^* each independently represents a straight-chain alkenyl radical having 2-6 C atoms. Alkenyl and alkenyl ^* preferably denote CH ₂ =CH-, CH ₂ =CHCH ₂ CH ₂ -, CH ₃ -CH=CH-, CH ₃ -CH ₂ -CH=CH-,CH ₃ -(CH ₂ ) ₂ -CH=CH-, CH ₃ -(CH ₂ ) ₃ -CH=CH- or CH ₃ -CH=CH-(CH ₂ ) ₂ -.

d)另外包含一或多種下式之化合物的LC介質： d) LC medium additionally comprising one or more compounds of the formula:

其中個別基團具有以下含義：表示或f表示0或1；R¹ 及R² 彼此獨立地各自表示具有1至12個C原子的烷基，此外，其中一或兩個非相鄰CH₂ 基團可以O原子彼此間不直接相連之方式經－O－、－CH＝CH－、－CO－、－OCO－或－COO－置換；Z^x 及Z^y 彼此獨立地各自表示－CH₂ CH₂ －、－CH＝CH－、－CF₂ O－、－OCF₂ －、－CH₂ O－、－OCH₂ －、－COO－、－OCO－、－C₂ F₄ －、－CF＝CF－、－CH＝CHCH₂ O－或單鍵，較佳表示單鍵；L¹ 及L² 彼此獨立地各自表示F、Cl、OCF₃ 、CF₃ 、CH₃ 、CH₂ F、CHF₂ 。Some of these groups have the following meanings: Express or f represents 0 or 1; R ¹ and R ² each independently represent an alkyl group having 1 to 12 C atoms, and further, one or two non-adjacent CH ₂ groups may have O atoms not directly connected to each other. The mode is replaced by -O-, -CH=CH-, -CO-, -OCO- or -COO-; Z ^x and Z ^y each independently represent -CH ₂ CH ₂ -, -CH=CH-, -CF ₂ O-, -OCF ₂ -, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -C ₂ F ₄ -, -CF=CF-, -CH=CHCH ₂ O- or single The bond preferably represents a single bond; L ¹ and L ² each independently represent F, Cl, OCF ₃ , CF ₃ , CH ₃ , CH ₂ F, CHF ₂ .

較佳地，基團L¹ 與L² 皆表示F，或基團L¹ 與L² 中一者表示F且另一者表示Cl。Preferably, both groups L ¹ and L ² represent F, or one of the groups L ¹ and L ² represents F and the other represents Cl.

式LY之化合物較佳選自以下子式： The compound of formula LY is preferably selected from the following subtypes:

其中R¹ 具有上述含義，且v表示1至6之整數。R¹ 較佳表示直鏈烷基或烯基，尤其CH₃ 、C₂ H₅ 、n－C₃ H₇ 、n－C₄ H₉ 、n－C₅ H₁₁ 、CH₂ ＝CH－、CH₂ ＝CHCH₂ CH₂ －、CH₃ －CH＝CH－、CH₃ －CH₂ －CH＝CH－、CH₃ －(CH₂ )₂ －CH＝CH－、CH₃ －(CH₂ )₃ －CH＝CH－或CH₃ －CH＝CH－(CH₂ )₂ －。Wherein R ¹ has the above meaning, and v represents an integer of 1 to 6. R ¹ preferably denotes a linear alkyl or alkenyl group, especially CH ₃ , C ₂ H ₅ , n-C ₃ H ₇ , n-C ₄ H ₉ , n-C ₅ H ₁₁ , CH ₂ =CH-, CH ₂ =CHCH ₂ CH ₂ -,CH ₃ -CH=CH-, CH ₃ -CH ₂ -CH=CH-, CH ₃ -(CH ₂ ) ₂ -CH=CH-,CH ₃ -(CH ₂ ) ₃ - CH=CH- or CH ₃ -CH=CH-(CH ₂ ) ₂ -.

e)另外包含一或多種選自下式之化合物的LC介質： e) an LC medium additionally comprising one or more compounds selected from the group consisting of:

其中烷基表示C_1－6 烷基，L表示H或F，且X表示F、Cl、 OCF₃ 、OCHF₂ 或OCH＝CF₂ 。尤其較佳為其中X表示F的式G1化合物。Wherein alkyl represents C _1-6 alkyl, L represents H or F, and X represents F, Cl, OCF ₃ , OCHF ₂ or OCH=CF ₂ . Especially preferred are compounds of formula G1 wherein X represents F.

f)另外包含一或多種選自下式之化合物的LC介質： f) an LC medium additionally comprising one or more compounds selected from the group consisting of:

其中R⁵ 具有如上針對R¹ 所指明之含義之一，烷基表示C_1－6 烷基，d表示0或1，且z及m彼此獨立地各自表示1至6之整數。該等化合物中之R⁵ 尤其較佳為C_1－6 烷基或C_1－6 烷氧基或C_2－6 烯基，d較佳為1。本發明之LC介質較佳包含5 wt%之量之上述式之一或多種化合物。Wherein R ⁵ has ^one of the meanings indicated above for R ¹ , alkyl represents C _1-6 alkyl, d represents 0 or 1, and z and m each independently represent an integer from 1 to 6. R ^{5 in} these compounds is particularly preferably a C _1-6 alkyl group or a C _1-6 alkoxy group or a C _2-6 alkenyl group, and d is preferably 1. The LC medium of the present invention preferably comprises One or more compounds of the above formula in an amount of 5 wt%.

g)另外包含一或多種下式之聯苯化合物的LC介質： g) an LC medium additionally comprising one or more biphenyl compounds of the formula:

式B1至B3之聯苯在LC混合物中之比例較佳為至少3 wt%，尤其5 wt%。The proportion of biphenyl of formula B1 to B3 in the LC mixture is preferably at least 3 wt%, especially 5 wt%.

式B2之化合物尤其較佳。Compounds of formula B2 are especially preferred.

式B1至B3之化合物較佳選自以下子式： The compounds of formula B1 to B3 are preferably selected from the following subtypes:

其中烷基^＊表示具有1－6個C原子的烷基。本發明之介質尤其較佳包含式B1a及/或B2c之一或多種化合物。Wherein alkyl ^* represents an alkyl group having 1 to 6 C atoms. The medium of the invention particularly preferably comprises one or more compounds of the formula B1a and/or B2c.

h)另外包含一或多種下式之聯三苯化合物的LC介質： h) an LC medium additionally comprising one or more triphenyl compounds of the formula:

其中R⁵ 及R⁶ 彼此獨立地各自具有如上針對R¹ 所指明之含義之一，且及彼此獨立地各自表示或其中L⁵ 表示F或Cl，較佳F，且L⁶ 表示F、Cl、OCF₃ 、CF₃ 、CH₃ 、CH₂ F或CHF₂ ，較佳表示F。Wherein R ⁵ and R ⁶ each independently of one another have one of the meanings indicated above for R ¹ , and and Respectively independent of each other or Wherein L ⁵ represents F or Cl, preferably F, and L ⁶ represents F, Cl, OCF ₃ , CF ₃ , CH ₃ , CH ₂ F or CHF ₂ , preferably F.

式T之化合物較佳選自以下子式：其中R表示具有1－7個C原子的直鏈烷基或烷氧基，R^＊表示具有2－7個C原子的直鏈烯基，且m表示1至6之整數。 R^＊較佳表示CH₂ ＝CH－、CH₂ ＝CHCH₂ CH₂ －、CH₃ －CH＝CH－、CH₃ －CH₂ －CH＝CH－、CH₃ －(CH₂ )₂ －CH＝CH－、CH₃ －(CH₂ )₃ －CH＝CH－或CH₃ －CH＝CH－(CH₂ )₂ －。The compound of formula T is preferably selected from the following subtypes: Wherein R represents a linear alkyl group or alkoxy group having 1 to 7 C atoms, R ^* represents a linear alkenyl group having 2 to 7 C atoms, and m represents an integer of 1 to 6. R ^* preferably represents CH ₂ =CH-, CH ₂ =CHCH ₂ CH ₂ -, CH ₃ -CH=CH-, CH ₃ -CH ₂ -CH=CH-, CH ₃ -(CH ₂ ) ₂ -CH= CH-, CH ₃ -(CH ₂ ) ₃ -CH=CH- or CH ₃ -CH=CH-(CH ₂ ) ₂ -.

R較佳表示甲基、乙基、丙基、丁基、戊基、己基、甲氧基、乙氧基、丙氧基、丁氧基或戊氧基。R preferably represents a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group or a pentyloxy group.

本發明之LC介質較佳包含2－30 wt%、尤其5－20 wt%之量之式T及其較佳子式之聯三苯。The LC medium of the present invention preferably comprises from 2 to 30% by weight, especially from 5 to 20% by weight, of the formula T and its preferred form of terphenyl.

尤其較佳為式T1、T2、T3及T21之化合物。在該等化合物中，R較佳表示各自具有1－5個C原子的烷基及烷氧基。Particularly preferred are compounds of the formulae T1, T2, T3 and T21. In these compounds, R preferably represents an alkyl group and an alkoxy group each having 1 to 5 C atoms.

若欲混合物之△n值0.1，則本發明之混合物中較佳使用聯三苯。較佳混合物包含2－20 wt%之式T之一或多種聯三苯化合物，較佳選自化合物T1至T22之群。If you want the Δn value of the mixture 0.1, diphenylbenzene is preferably used in the mixture of the present invention. Preferably, the mixture comprises from 2 to 20% by weight of one or more biphenyl compounds of the formula T, preferably selected from the group of compounds T1 to T22.

i)另外包含一或多種以下式之化合物的LC介質： i) LC medium additionally comprising one or more compounds of the formula:

其中R¹ 及R² 具有上述含義且較佳彼此獨立地各自表示直鏈烷基或烯基。Wherein R ¹ and R ² have the above meanings and preferably each independently represent a linear alkyl group or an alkenyl group.

較佳介質包含一或多種選自式O1、O3及O4的化合物。Preferred media comprise one or more compounds selected from the group consisting of formulas O1, O3 and O4.

k)另外包含較佳>3 wt%、尤其5 wt%且極其較佳5－30 wt%之量之一或多種下式之化合物的LC介質： k) additionally comprising preferably >3 wt%, especially LC medium of one or more compounds of the formula: 5 wt% and very preferably 5-30 wt%:

其中：表示 among them: Express

R⁹ 表示H、CH₃ 、C₂ H₅ 或n－C₃ H₇ ，且q表示1、2或3，且R⁷ 具有針對R¹ 所指明之含義之一。R ⁹ represents H, CH ₃ , C ₂ H ₅ or n-C ₃ H ₇ , and q represents 1, 2 or 3, and R ⁷ has ^one of the meanings indicated for R ¹ .

尤其較佳的式IF化合物選自以下子式： Particularly preferred compounds of formula IF are selected from the following subtypes:

其中R⁷ 較佳表示直鏈烷基，且R⁹ 表示CH₃ 、C₂ H₅ 或n－C₃ H₇ 。尤其較佳為式FI1、FI2及FI3之化合物。Wherein R ⁷ preferably represents a linear alkyl group, and R ⁹ represents CH ₃ , C ₂ H ₅ or n-C ₃ H ₇ . Particularly preferred are compounds of the formulae FI1, FI2 and FI3.

m)另外包含一或多種下式之化合物的LC介質： m) an LC medium additionally comprising one or more compounds of the formula:

其中R⁸ 具有針對R¹ 所指明之含義，且烷基表示具有1－6個C原子的直鏈烷基。Wherein R ⁸ has the meaning indicated for R ¹ and alkyl represents a straight-chain alkyl group having 1 to 6 C atoms.

n)另外包含一或多種含有四氫萘基或萘基單元之化合物(例如選自下式的化合物)的LC介質： n) an LC medium additionally comprising one or more compounds containing tetrahydronaphthyl or naphthyl units, for example a compound selected from the group consisting of:

其中R¹⁰ 及R¹¹ 彼此獨立地各自具有針對R¹ 所指明之含義之一，較佳表示直鏈烷基、直鏈烷氧基或直鏈烯基，且Z、Z¹ 及Z² 彼此獨立地各自表示－C₂ H₄ －、－CH＝CH－、－(CH₂ )₄ －、－(CH₂ )₃ O－、－O(CH₂ )₃ －、－CH＝CHCH₂ CH₂ －、－CH₂ CH₂ CH＝CH－、－CH₂ O－、－OCH₂ －、－COO－、－OCO－、－C₂ F₄ －、－CF＝CF－、－CF＝CH－、－CH＝CF－、－CH₂ －或單鍵。Wherein R ¹⁰ and R ¹¹ each independently have ^one of the meanings indicated for R ¹ , preferably a linear alkyl group, a linear alkoxy group or a linear alkenyl group, and Z, Z ¹ and Z ² are independent of each other. Each represents -C ₂ H ₄ -, -CH=CH-, -(CH ₂ ) ₄ -, -(CH ₂ ) ₃ O-, -O(CH ₂ ) ₃ -, -CH=CHCH ₂ CH ₂ - , -CH ₂ CH ₂ CH=CH-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -C ₂ F ₄ -, -CF=CF-, -CF=CH-, - CH=CF-, -CH ₂ - or a single bond.

o)另外包含較佳3至20 wt%之量、尤其3至15 wt%之量之一或多種下式之二氟二苯并色滿及/或色滿的LC介質： o) additionally comprising, in an amount of preferably from 3 to 20% by weight, in particular from 3 to 15% by weight, of one or more of the difluorodibenzochroman and/or chroma LC media of the formula:

其中R¹¹ 及R¹² 彼此獨立地各自具有上述含義，且c表示0或1。Wherein R ¹¹ and R ¹² each independently have the above meanings, and c represents 0 or 1.

尤其較佳之式BC及CR化合物選自以下子式： Particularly preferred formulas BC and CR compounds are selected from the following subtypes:

其中烷基及烷基^＊彼此獨立地各自表示具有1－6個C原子的直鏈烷基，且烯基及烯基^＊彼此獨立地各自表示具有2－6個C原子的直鏈烯基。烯基及烯基^＊較佳表示 CH₂ ＝CH－、CH₂ ＝CHCH₂ CH₂ －、CH₃ －CH＝CH－、CH₃ －CH₂ －CH＝CH－、CH₃ －(CH₂ )₂ －CH＝CH－、CH₃ －(CH₂ )₃ －CH＝CH－或CH₃ －CH＝CH－(CH₂ )₂ －。Wherein the alkyl and alkyl ^* each, independently represents a linear alkyl group having 1-6 C atoms, and alkenyl and alkenyl ^* each independently represents a straight-chain alkenyl radical having 2-6 C atoms. Alkenyl and alkenyl ^* preferably denote CH ₂ =CH-, CH ₂ =CHCH ₂ CH ₂ -, CH ₃ -CH=CH-, CH ₃ -CH ₂ -CH=CH-,CH ₃ -(CH ₂ ) ₂ -CH=CH-, CH ₃ -(CH ₂ ) ₃ -CH=CH- or CH ₃ -CH=CH-(CH ₂ ) ₂ -.

極其較佳為包含一、二或三種式BC－2之化合物的混合物。Very preferably a mixture comprising one, two or three compounds of the formula BC-2.

p)另外包含一或多種下式之氟化菲或二苯并呋喃的LC介質： p) an LC medium additionally comprising one or more fluorinated phenanthrene or dibenzofuran of the formula:

其中R¹¹ 及R¹² 彼此獨立地各自具有上述含義，b表示0或1，L表示F，且r表示1、2或3。Wherein R ¹¹ and R ¹² each independently have the above meanings, b represents 0 or 1, L represents F, and r represents 1, 2 or 3.

尤其較佳之式PH及BF化合物選自以下子式： Particularly preferred forms of the PH and BF compounds are selected from the following subtypes:

其中R及R'彼此獨立地各自表示具有1－7個C原子的直鏈烷基或烷氧基。Wherein R and R' each independently represent a linear alkyl group or alkoxy group having 1 to 7 C atoms.

q)包含一或多種下式之化合物、較佳用於PSA－OCB顯示器的LC介質： q) LC medium comprising one or more compounds of the formula, preferably for PSA-OCB displays:

其中：R⁰ 各自出現時相同或不同地表示各自具有至多9個C原子的正烷基、烷氧基、氧雜烷基、氟烷基或烯基；X⁰ 表示F、Cl，或各種情況下之各自具有至多6個C原子的鹵化烷基、烯基、烯氧基或烷氧基；Z⁰ 表示－CF₂ O－或單鍵；Y^1－6 彼此獨立地各自表示H或F。Wherein: R ⁰ each appears identically or differently to an n-alkyl, alkoxy, oxaalkyl, fluoroalkyl or alkenyl group each having up to 9 C atoms; X ⁰ represents F, Cl, or various conditions Lower alkyl, alkenyl, alkenyloxy or alkoxy groups each having up to 6 C atoms; Z ⁰ represents -CF ₂ O- or a single bond; Y ^1-6 each independently represents H or F.

X⁰ 較佳為F、Cl、CF₃ 、CHF₂ 、OCF₃ 、OCHF₂ 、OCFHCF₃ 、OCFHCHF₂ 、OCFHCHF₂ 、OCF₂ CH₃ 、 OCF₂ CHF₂ 、OCF₂ CHF₂ 、OCF₂ CF₂ CHF₂ 、OCF₂ CF₂ CHF₂ 、OCFHCF₂ CF₃ 、OCFHCF₂ CHF₂ 、OCF₂ CF₂ CF₃ 、OCF₂ CF₂ CClF₂ 、OCClFCF₂ CF₃ 或CH＝CF₂ ，尤其較佳為F或OCF₃ 。X ⁰ is preferably _{F, Cl, CF 3, CHF} 2, OCF 3, OCHF 2, OCFHCF 3, OCFHCHF 2, OCFHCHF 2, OCF 2 CH 3, OCF 2 CHF 2, OCF 2 CHF 2, OCF 2 CF 2 CHF _{_{_{_{2, OCF 2 CF 2 CHF 2}}}} , OCFHCF 2 CF 3, OCFHCF 2 CHF 2, OCF 2 CF 2 CF 3, OCF 2 CF 2 CClF 2, OCClFCF 2 CF 3 or CH = CF _2, particularly preferably F or OCF ₃ .

式AA化合物較佳選自以下式： The compound of formula AA is preferably selected from the following formula:

其中R⁰ 及X⁰ 具有上述含義，且X⁰ 較佳表示F。尤其較佳為式AA2及AA6之化合物。Wherein R ⁰ and X ⁰ have the above meanings, and X ⁰ preferably represents F. Particularly preferred are compounds of the formulae AA2 and AA6.

式BB化合物較佳選自以下式： The compound of formula BB is preferably selected from the following formula:

其中R⁰ 及X⁰ 具有上述含義，且X⁰ 較佳表示F。尤其較佳為式BB1、BB2及BB5之化合物。Wherein R ⁰ and X ⁰ have the above meanings, and X ⁰ preferably represents F. Particularly preferred are compounds of the formulae BB1, BB2 and BB5.

式CC化合物較佳選自以下式： The compound of the formula CC is preferably selected from the following formula:

其中R⁰ 在各自出現時相同或不同地具有上述含義且較佳表示具有1至6個C原子的烷基。Wherein R ⁰ has the same meaning as defined above or differently and preferably represents an alkyl group having 1 to 6 C atoms.

r)除式I或其子式之可聚合化合物及共聚單體外，不包含含有末端乙烯基或乙烯氧基(－CH＝CH₂ 、－O－CH＝CH₂ )之化合物的LC介質。r) An LC medium containing a compound having a terminal vinyl group or a vinyloxy group (-CH=CH ₂ , -O-CH=CH ₂ ) other than the polymerizable compound of the formula I or its subformulae and a comonomer.

s)包含1至5種、較佳1、2或3種可聚合化合物的LC介質。s) an LC medium comprising from 1 to 5, preferably 1, 2 or 3 polymerizable compounds.

t)其中可聚合化合物在整個混合物中之比例為0.05至5%、較佳為0.1至1%的LC介質。t) an LC medium in which the proportion of the polymerizable compound in the entire mixture is from 0.05 to 5%, preferably from 0.1 to 1%.

u)包含1至8種、較佳1至5種式CY1、CY2、PY1及/或PY2之化合物的LC介質。該等化合物在整個混合物中的比例較佳為5至60%，尤其較佳10至35%。在各種情況下，該等個別化合物之含量較佳為2至20%。u) LC medium comprising from 1 to 8, preferably from 1 to 5 compounds of the formula CY1, CY2, PY1 and/or PY2. The proportion of the compounds in the entire mixture is preferably from 5 to 60%, particularly preferably from 10 to 35%. In each case, the content of the individual compounds is preferably from 2 to 20%.

v)包含1至8種、較佳1至5種式CY9、CY10、PY9及/或PY10之化合物的LC介質。該等化合物在整個混合物中的比例較佳為5至60%，尤其較佳10至35%。在各種情況下，該等個別化合物之含量較佳為2至20%。v) LC medium comprising from 1 to 8, preferably from 1 to 5 compounds of the formula CY9, CY10, PY9 and/or PY10. The proportion of the compounds in the entire mixture is preferably from 5 to 60%, particularly preferably from 10 to 35%. In each case, the content of the individual compounds is preferably from 2 to 20%.

w)包含1至10種、較佳1至8種式ZK化合物、尤其式ZK1、ZK2及/或ZK6之化合物的LC介質。該等化合物在整個混合物中的比例較佳為3至25%，尤其較佳5至45%。在各種情況下，該等個別化合物之含量較佳為2至20%。w) LC medium comprising from 1 to 10, preferably from 1 to 8, compounds of the formula ZK, in particular compounds of the formula ZK1, ZK2 and/or ZK6. The proportion of the compounds in the entire mixture is preferably from 3 to 25%, particularly preferably from 5 to 45%. In each case, the content of the individual compounds is preferably from 2 to 20%.

x)其中式CY、PY及ZK之化合物在整個混合物中的比例大於70%、較佳大於80%的LC介質。x) LC medium in which the proportion of the compounds of the formula CY, PY and ZK is greater than 70%, preferably greater than 80%, of the total mixture.

y)另外較佳以表B所提供之濃度範圍包含一或多種較佳低分子量且/或不可聚合之對掌性摻雜劑(選自表B極佳)的LC介質。y) Further preferably, the concentration range provided in Table B comprises one or more preferred low molecular weight and/or non-polymerizable palmitic dopants (exceeding from Table B).

上述較佳實施例a)－x)之化合物與上述聚合化合物之組合使本發明之LC介質在維持高清晰點及高HR值的同時、達成低臨限電壓、低旋轉黏度及優良的低溫穩定性，且容許在PS(A)顯示器中設定預傾角。特定而言，與先前技術的介質相比，PS(A)顯示器中的LC介質呈現大大縮短的響應時間，尤其亦呈現大大縮短的灰影響應時間。The combination of the compound of the above preferred embodiments a)-x) and the above polymeric compound enables the LC medium of the present invention to achieve a low threshold voltage, a low rotational viscosity and an excellent low temperature stability while maintaining a high definition point and a high HR value. And allows the pretilt angle to be set in the PS (A) display. In particular, LC media in PS(A) displays exhibit significantly reduced response times compared to prior art media, and in particular also exhibit greatly reduced ash effects.

液晶混合物較佳具有至少80 K、尤其較佳至少100 K之向列相範圍，及在20℃下不大於250 mPa．s、較佳不大於200 mPa．s的旋轉黏度。The liquid crystal mixture preferably has a nematic phase range of at least 80 K, particularly preferably at least 100 K, and no more than 250 mPa at 20 °C. s, preferably no more than 200 mPa. The rotational viscosity of s.

用於VA型顯示器的本發明之LC介質在20℃及1 kHz下具有負介電各向異性△ε，較佳約－0.5至－7.5、尤其約－2.5至－5.5之△ε。The LC medium of the present invention for a VA type display has a temperature of 20 ° C and 1 kHz There is a negative dielectric anisotropy Δ ε, preferably about -0.5 to -7.5, especially about Δ ε of -2.5 to -5.5.

用於OCB型顯示器之本發明之LC介質在20℃及1 kHz下具有正介電各向異性△ε，較佳約＋7至＋17之△ε。The LC medium of the present invention for an OCB type display has a positive dielectric anisotropy Δ ε at 20 ° C and 1 kHz, preferably Δ ε of about +7 to +17.

用於VA型顯示器之本發明之LC介質之雙折射率△n較佳小於0.16，尤其較佳介於0.06與0.14之間，尤其介於0.07與0.12之間。The birefringence Δn of the LC medium of the present invention for a VA type display is preferably less than 0.16, particularly preferably between 0.06 and 0.14, especially between 0.07 and 0.12.

用於OCB型顯示器之本發明之LC介質之雙折射率△n較佳介於0.14與0.22之間，尤其介於0.16與0.22之間。The birefringence Δn of the LC medium of the present invention for an OCB type display is preferably between 0.14 and 0.22, especially between 0.16 and 0.22.

電介質亦可包含熟習此項技術者已知且描述於文獻中的其他添加劑。舉例而言，可添加0至15 wt%之多向色染料，此外可添加奈米顆粒、傳導性鹽(較佳乙基二甲基十二烷基4－己氧基苯甲酸銨、四丁基四苯基硼酸銨或冠醚之錯合鹽)(參見例如Haller等人，Mol.Cryst.Liq.Cryst.24 ,249－258(1973))以便改良傳導性，或可添加物質以便修改介電各向異性、黏度及/或向列相之對準。此類物質描述於例如DE－A 22 09 127、22 40 864、23 21 632、23 38 281、24 50 088、26 37 430及28 53 728。The dielectric may also contain other additives known to those skilled in the art and described in the literature. For example, 0 to 15 wt% of the polychromic dye may be added, in addition, nano particles, conductive salts (preferably ethyl dimethyldodecylate 4-hexyloxybenzoic acid ammonium, tetrabutyl) may be added. a mis-synthesis salt of ammonium tetraphenylborate or a crown ether) (see, for example, Haller et al., Mol. Cryst. Liq. Cryst. 24 , 249-258 (1973)) in order to improve conductivity, or may add substances for modification. Alignment of electrical anisotropy, viscosity, and/or nematic phase. Such materials are described, for example, in DE-A 22 09 127, 22 40 864, 23 21 632, 23 38 281, 24 50 088, 26 37 430 and 28 53 728.

本發明之LC介質之較佳實施例a)－x)之個別組分已知，或其製備方式易由相關技術者依據先前技術獲得，因為該等製備方式係基於文獻中所述的標準方法。式CY之相應化合物描述於例如EP－A－0 364 538中。式ZK之相應化合物描述於例如DE－A－26 36 684及DE－A－33 21 373中。The individual components of the preferred embodiments a)-x) of the LC medium of the present invention are known, or the manner of their preparation is readily obtained by the skilled artisan based on prior art, since such preparation is based on standard methods described in the literature. . Corresponding compounds of the formula CY are described, for example, in EP-A-0 364 538. Corresponding compounds of the formula ZK are described, for example, in DE-A-26 36 684 and DE-A-33 21 373.

可根據本發明使用的LC介質以本來習知的方式(例如將一或多種上述化合物與一或多種如上定義的可聚合化合物混合且視需要與其他液晶化合物及/或添加劑混合)製備。一般而言，最好在高溫下，將所要量之以較少量使用的組分溶於構成主成分的組分中。亦可將該等組分於有機溶劑(例如丙酮、氯仿或甲醇)中之溶液混合，並在充分混合後，藉由例如蒸餾再將溶劑移除。本發明此外係關於製備本發明之LC介質的方法。The LC medium that can be used in accordance with the present invention is in a manner conventional in the art (eg, One or more of the above compounds are prepared by mixing with one or more polymerizable compounds as defined above and optionally mixed with other liquid crystal compounds and/or additives. In general, it is preferred to dissolve the components to be used in a smaller amount in a component constituting the main component at a high temperature. The components may also be mixed in a solution in an organic solvent such as acetone, chloroform or methanol, and after thorough mixing, the solvent is removed by, for example, distillation. The invention further relates to a process for preparing an LC medium of the invention.

對於熟習此項技術者顯而易見的是，本發明之LC介質亦可包含其中例如H、N、O、CI、F已經相應同位素置換的化合物。It will be apparent to those skilled in the art that the LC media of the present invention may also comprise compounds in which, for example, H, N, O, CI, F have been correspondingly isotopically substituted.

本發明之LC顯示器之結構類似於如開篇所引用之先前技術中所述之PS(A)顯示器的習知幾何結構。較佳為無突起的幾何結構，此外，尤其較佳為其中位於濾色器側之電極非結構化且僅位於TFT側之電極具有狹縫的彼等幾何結構。PSA－VA顯示器之尤其適當且較佳的電極結構描述於例如US 2006/0066793 A1中。The structure of the LC display of the present invention is similar to the conventional geometry of a PS (A) display as described in the prior art cited in the opening paragraph. A geometry having no protrusions is preferred, and in addition, it is particularly preferred that the electrodes on the side of the color filter are unstructured and that only the electrodes on the side of the TFT have slits. Particularly suitable and preferred electrode structures for PSA-VA displays are described, for example, in US 2006/0066793 A1.

以下實例說明本發明而非限定其。然而，其向熟習此項技術者展示具有使用起來較佳之化合物的較佳混合物概念及其相應濃度及其彼此間之組合。此外，該等實例說明可達成哪些特性及特性組合。The following examples illustrate the invention without limiting it. However, it is shown to those skilled in the art that the preferred mixture concept of the compounds which are preferred for use and their respective concentrations and combinations thereof. In addition, these examples illustrate what characteristics and combinations of features can be achieved.

使用以下縮寫及簡稱：(n、m、z彼此獨立地各自表示1、2、3、4、5或6)The following abbreviations and abbreviations are used: (n, m, z each independently represent 1, 2, 3, 4, 5 or 6)

在本發明之一較佳實施例中，本發明之LC介質包含一或多種選自由表A之化合物組成之群的化合物。In a preferred embodiment of the invention, the LC medium of the present invention comprises a Or a plurality of compounds selected from the group consisting of the compounds of Table A.

LC介質較佳包含0至10 wt%、尤其0.01至5 wt%且尤其較佳0.1至3 wt%之摻雜劑。LC介質較佳包含一或多種選自由表B之化合物組成之群的摻雜劑。The LC medium preferably comprises from 0 to 10% by weight, especially from 0.01 to 5% by weight and particularly preferably from 0.1 to 3% by weight of dopant. The LC medium preferably comprises one or more dopants selected from the group consisting of the compounds of Table B.

LC介質較佳包含0至10 wt%、尤其0.01至5 wt%且尤其較佳0.1至3 wt%之穩定劑。LC介質較佳包含一或多種選自由表C之化合物組成之群的穩定劑。The LC medium preferably comprises from 0 to 10% by weight, especially from 0.01 to 5% by weight and particularly preferably from 0.1 to 3% by weight of stabilizer. The LC medium preferably comprises one or more stabilizers selected from the group consisting of the compounds of Table C.

此外：V_o 表示在20℃下的電容式臨限電壓；n_e 表示在20℃及589 nm下的非尋常折射率；n_o 表示在20℃及589 nm下的尋常折射率；△n表示在20℃及589 nm下的光學各向異性；ε_⊥ 表示在20℃及1 kHz下垂直於引向器的電介質電納係數；ε_∥ 表示在20┴及1 kHz下平行於引向器的電介質電納係數；△ε表示在20℃及1 kHz下的介電各向異性；cl.p.,T(N,I)表示清晰點[℃]；γ₁ 表示在20℃下的旋轉黏度[mPa．s]；K₁ 表示在20℃下之"展曲"形變的彈性常數[pN]；K₂ 表示在20℃下之"扭曲"形變的彈性常數[pN]；K₃ 表示在20℃下之"彎曲"形變的彈性常數[pN]；LTS表示在測試單元中測定的低溫穩定性(相)；HR₂₀ 表示在20℃下的電壓保持比[%]，且HR₁₀₀ 表示在100℃下的電壓保持比[%]。In addition: V _o represents the capacitive threshold voltage at 20 ° C; n _e represents the extraordinary refractive index at 20 ° C and 589 nm; n _o represents the ordinary refractive index at 20 ° C and 589 nm; Δn represents Optical anisotropy at 20 ° C and 589 nm; ε _⊥ represents the dielectric susceptance of the director perpendicular to the director at 20 ° C and 1 kHz; ε _∥ is parallel to the director at 20 ┴ and 1 kHz Dielectric susceptance coefficient; △ ε represents dielectric anisotropy at 20 ° C and 1 kHz; cl.p., T (N, I) represents a clear point [°C]; γ ₁ represents a rotational viscosity at 20 ° C [mPa. s]; K ₁ represents the elastic constant [pN] of the "bend" deformation at 20 ° C; K ₂ represents the elastic constant [pN] of the "twisted" deformation at 20 ° C; K ₃ represents at 20 ° C "Bending" deformation elastic constant [pN]; LTS indicates low temperature stability (phase) measured in the test unit; HR ₂₀ indicates voltage holding ratio [%] at 20 ° C, and HR ₁₀₀ indicates at 100 ° C Voltage hold ratio [%].

除非另明確說明，否則本申請案中的所有濃度以wt%指明且係關於相應混合物或混合物組分，除非另明確指明。All concentrations in this application are indicated in wt% and are for the respective mixtures or mixture components unless otherwise specifically indicated.

除非另明確說明，否則本申請案中所指明的所有溫度值(諸如熔點T(C,N)、近晶相至向列相T(S,N)轉移溫度及清晰點T(N,I))皆以攝氏溫度(℃)指明。All temperature values specified in this application (such as melting point T (C, N), smectic phase to nematic phase T (S, N) transfer temperature and sharp point T (N, I) unless otherwise stated otherwise) ) are indicated in degrees Celsius (°C).

所有物理特性皆根據以下文獻測定"Merck Liquid Crystals,Physical Properties of Liquid Crystals",Status Nov.1997,Merck KGaA,Germany,且適於20℃之溫度，且△n係在589 nm下測定且△ε係在1 kHz下測定，除非在各種情況下另明確指明。All physical properties were determined according to the following literature "Merck Liquid Crystals, Physical Properties of Liquid Crystals", Status Nov. 1997, Merck KGaA, Germany, and suitable for temperatures of 20 ° C, and Δn is measured at 589 nm and Δε It is measured at 1 kHz unless otherwise specified in each case.

對於本發明，術語"臨限電壓"係關於電容式臨限值(V₀ )，亦稱Freedericksz臨限值，除非另明確指明。在該等實例中，正如通常所用，亦可指明10%相對對比度之光學臨限值(V₁₀ )。For the present invention, the term "threshold voltage" based on the capacitive threshold (V _0), also known as the Freedericksz threshold, unless explicitly indicated. In these examples, the optical threshold (V ₁₀ ) of 10% relative contrast can also be indicated, as is commonly used.

供量測電容式臨限電壓用的顯示器具有間距為4 μm的兩個平面平行外板及位於外板內部、上覆摩擦聚醯亞胺之對準層的電極層，從而產生液晶分子之各向同性邊緣對準。The display for measuring the capacitive threshold voltage has two plane parallel outer plates with a pitch of 4 μm and an electrode layer located inside the outer plate and overlying the alignment layer of the rubbing polyimide, thereby generating liquid crystal molecules. Align to the same edge.

可聚合化合物係在藉由UV照射預定時間的同時、經由對顯示器施加電壓(一般為10 V至30 V交流電，1 kHz)而在顯示器中聚合。在該等實例中，除非另外指明，否則使用28 mW/cm² 汞汽燈，使用裝配有365 nm帶通濾波器的標準UV儀(Ushio UNI型儀)量測強度。The polymerizable compound is polymerized in the display by applying a voltage to the display (typically 10 V to 30 V alternating current, 1 kHz) while being irradiated by UV for a predetermined time. In these examples, the intensity was measured using a 28 mW/cm ² mercury vapor lamp using a standard UV instrument (Ushio UNI model) equipped with a 365 nm bandpass filter, unless otherwise indicated.

藉由旋轉結晶實驗(Autronic－Melchers TBA－105)測定傾角。小值(亦即與90°角偏離較大)在此處對應於大的傾角。The tilt angle was measured by a rotary crystallization experiment (Autronic-Melchers TBA-105). A small value (i.e., a large deviation from the 90° angle) corresponds here to a large inclination.

實例1Example 1

4'－[3－(2－甲基丙烯醯氧基)丙氧基]聯苯－4－基2－甲基丙烯酸酯(1)如下製備：1.1. 4'－(3－羥基丙氧基)聯苯－4－醇 4'-[3-(2-Methylpropenyloxy)propoxy]biphenyl-4-yl 2-methacrylate (1) was prepared as follows: 1.1. 4'-(3-hydroxypropoxyl) Biphenyl-4-ol

將20.0 g(0.107 mol)之4,4'－二羥基聯苯、10.0 g(0.070 mol)之3－溴－1－丙醇及15.0 g(0.109 mol)碳酸鉀在回流下、於300 ml丙酮中加熱16小時。隨後將該批料過濾，且將濾液蒸發。將殘餘物溶解於MTB醚中，用水洗滌且經硫酸鈉乾燥。將溶劑真空移除，且使用甲苯/乙酸乙酯(1：1)將粗產物經由二氧化矽凝膠層析。自甲苯/乙酸乙酯中結晶，得到無色固體狀之4'－(3－羥基丙氧基)聯苯－4－醇。20.0 g (0.107 mol) of 4,4'-dihydroxybiphenyl, 10.0 g (0.070 mol) of 3-bromo-1-propanol and 15.0 g (0.109 mol) of potassium carbonate under reflux in 300 ml of acetone Heat in 16 hours. The batch was then filtered and the filtrate was evaporated. The residue was dissolved in MTB ether, washed with water and dried over sodium sulfate. The solvent was removed in vacuo and the crude material was chromatographed from silica gel using toluene/ethyl acetate (1:1). Crystallization from toluene/ethyl acetate gave 4'-(3-hydroxypropoxy)biphenyl-4-ol as a colorless solid.

1.2. 4'－[3－(2－甲基丙烯醯氧基)丙氧基]聯苯－4－基2－甲基丙烯酸酯1.2. 4'-[3-(2-Methylpropenyloxy)propoxy]biphenyl-4-yl 2-methacrylate

首先將4.50 g(18.4 mmol)之4'－(3－羥基丙氧基)聯苯－4－醇、6.5 ml(0.766 mol)甲基丙烯酸及0.5 g之N,N－二甲基胺基吡啶(DMAP)引入250 ml甲苯中，在冰冷卻下添加16.0 g(0.775 mol)N,N'－二環己基碳化二醯亞胺之溶液，且將混合物在室溫下攪拌隔夜。添加6.5 g草酸二水合物之後，將該批料攪拌1小時且過濾，且將濾液蒸發。使用庚烷/乙酸乙酯(2：1)將殘餘物經由二氧化矽凝膠過濾，且自***中再結晶，得到102℃熔點之無色晶體狀之3'－(2－甲基丙烯醯氧基)聯苯－3－基2－甲基丙烯酸酯。First, 4.50 g (18.4 mmol) of 4'-(3-hydroxypropoxy)biphenyl-4- Alcohol, 6.5 ml (0.766 mol) methacrylic acid and 0.5 g of N,N-dimethylaminopyridine (DMAP) were introduced into 250 ml of toluene, and 16.0 g (0.775 mol) of N, N'- was added under ice cooling. A solution of dicyclohexylcarbodiimide was stirred and the mixture was stirred overnight at room temperature. After adding 6.5 g of oxalic acid dihydrate, the batch was stirred for 1 hour and filtered, and the filtrate was evaporated. The residue was filtered through EtOAc (2:1) eluted with EtOAc (EtOAc:EtOAc) Biphenyl-3-yl 2-methacrylate.

實例2Example 2

4'－(2－甲基丙烯醯氧基甲基)聯苯－4－基2－甲基丙烯酸酯(2)如下製備：2.1. 4'－羥基甲基－4－聯苯酚 4'-(2-Methylpropenyloxymethyl)biphenyl-4-yl 2-methacrylate (2) was prepared as follows: 2.1. 4'-Hydroxymethyl-4-biphenol

將15.0 g(60.7 mmol)之4－羥基聯苯－4－甲酸乙酯溶於500 ml THF中，且在－70℃下添加二異丁基氫化鋁於甲苯中之1 M溶液200 ml。隨後移除冷卻浴，且將該批料在室溫下攪拌2小時。添加5 ml異丙醇之後，將該溶液添加至水中，用MTB醚萃取三次，且將所組合之有機相用水洗滌且經硫酸鈉乾燥。將溶劑真空移除，且使用甲苯/乙酸乙酯將殘餘物經由二氧化矽凝膠過濾，得到無色固體狀之4'－羥基甲基－4－聯苯酚。15.0 g (60.7 mmol) of ethyl 4-hydroxybiphenyl-4-carboxylate was dissolved in 500 ml of THF, and 200 ml of a 1 M solution of diisobutylaluminum hydride in toluene was added at -70 °C. The cooling bath was then removed and the batch was stirred at room temperature for 2 hours. After the addition of 5 ml of isopropanol, the solution was added to water, extracted three times with MTB ether, and the combined organic phases were washed with water and dried over sodium sulfate. The solvent was removed in vacuo and the residue was purified eluted with EtOAc EtOAc EtOAc Base-4-biphenol.

¹ H－NMR(DMSO－d₆ ,300 MHz)：δ＝4.51 ppm(s,2H,－CH₂ OH),5.13(s,br.，可交換，1 H,OH),6.83(AB－m_c ,2 H,Ar－H),7.34(AB－d,J＝8.3 Hz,2 H,Ar－H),7.46(AB－m_c ,2 H,Ar－H),7.52(AB－m_c ,2 H,Ar－H),9.51(s,br.，可交換，1 H,OH)。 ¹ H-NMR (DMSO-d ₆ , 300 MHz): δ = 4.51 ppm (s, 2H, -CH ₂ OH), 5.13 (s, br., exchange, 1 H, OH), 6.83 (AB-m _c , 2 H, Ar-H), 7.34 (AB-d, J = 8.3 Hz, 2 H, Ar-H), 7.46 (AB-m _c , 2 H, Ar-H), 7.52 (AB-m _c , 2 H, Ar-H), 9.51 (s, br., exchangeable, 1 H, OH).

2.2. 4'－(2－甲基丙烯醯氧基甲基)聯苯－4－基2－甲基丙烯酸酯2.2. 4'-(2-Methylpropenyloxymethyl)biphenyl-4-yl 2-methacrylate

使4'－羥基甲基－4－聯苯酚與甲基丙烯酸發生類似1.2.項下所述的酯化反應，得到71℃熔點之無色固體狀之4'－(2－甲基丙烯醯氧基甲基)聯苯－4－基2－甲基丙烯酸酯。The 4'-(2-methacryloxyloxy group) was obtained as a colorless solid with a melting point of 71 ° C, which was obtained by the esterification of 4'-hydroxymethyl-4-biphenol with methacrylic acid. Methyl)biphenyl-4-yl 2-methacrylate.

實例3Example 3

類似於實例2製備4'－(丙烯醯氧基甲基)聯苯－4－基丙烯酸酯(3) Preparation of 4'-(acryloxymethyl)biphenyl-4-yl acrylate similar to Example 2 (3)

獲得62℃熔點之無色晶體狀之4'－(丙烯醯氧基甲基)聯苯－4－基丙烯酸酯。4'-(acryloxymethyl)biphenyl-4-yl acrylate was obtained as a colorless crystal at 62 ° C.

以下化合物由可市購前驅物、類似於實例1獲得。The following compounds were obtained from commercially available precursors, similar to Example 1.

實例4Example 4

類似於實例1製備3－[4－(2－甲基丙烯醯氧基)苯氧基]丙基 2－甲基丙烯酸酯(4) 得到58℃熔點之無色晶體。Preparation of 3-[4-(2-methylpropenyloxy)phenoxy]propyl 2-methacrylate similar to Example 1 (4) A colorless crystal having a melting point of 58 ° C was obtained.

實例5Example 5

類似於實例1製備6－[3－(2－甲基丙烯醯氧基)丙氧基]萘－2－基2－甲基丙烯酸酯(5) 得到68℃熔點之無色晶體。Preparation of 6-[3-(2-methylpropenyloxy)propoxy]naphthalen-2-yl 2-methacrylate (5) similar to Example 1. A colorless crystal having a melting point of 68 ° C was obtained.

實例6Example 6

類似於實例2製備3－[4'－(2－甲基丙烯醯氧基)聯苯－4－基]丙基2－甲基丙烯酸酯(6) 得到69℃熔點之無色晶體。Preparation of 3-[4'-(2-methylpropenyloxy)biphenyl-4-yl]propyl 2-methacrylate (6) analogously to Example 2. A colorless crystal having a melting point of 69 ° C was obtained.

實例7Example 7

類似於實例2製備2－[4'－(2－甲基丙烯醯氧基)聯苯－4－基]乙基2－甲基丙烯酸酯(7) 得到108℃熔點之無色晶體。Preparation of 2-[4'-(2-methylpropenyloxy)biphenyl-4-yl]ethyl 2-methacrylate (7) analogously to Example 2. A colorless crystal having a melting point of 108 ° C was obtained.

實例8Example 8

將化合物(1)及(5)之溶解度與獲知於先前技術(例如EP 1 498 468 A1)之不含間隔基之結構類似化合物(A)及(B)之溶解度相比： The solubility of compounds (1) and (5) is compared to the solubility of structurally similar compounds (A) and (B) which are known to the prior art (for example EP 1 498 468 A1) without spacers:

為此，在50℃攪拌(1/2小時)下將各種化合物以5 wt%之濃度溶於可市購的向列型LC混合物LCT－06－441(Merck KGaA,Darmstadt)中，且接著不攪拌而冷卻至室溫。結果：(1)：在室溫下隔夜結晶析出(5)：在室溫下隔夜稍微結晶析出(A)：冷卻至室溫時立刻結晶析出(C)：冷卻至室溫時立刻結晶析出。To this end, various compounds were dissolved in a commercially available nematic LC mixture LCT-06-441 (Merck KGaA, Darmstadt) at a concentration of 5 wt% with stirring at 50 ° C (1/2 hour), and then Stir and cool to room temperature. Results: (1): Crystallization was precipitated overnight at room temperature (5): crystallized slightly at room temperature overnight (A): crystallized immediately after cooling to room temperature (C): crystallized immediately after cooling to room temperature.

與先前技術不含間隔基的化合物相比，含有間隔基之本發明之化合物呈現明顯更佳的溶解度。The compounds of the invention containing a spacer exhibit significantly better solubility than the prior art compounds which do not contain a spacer.

實例9－混合物實例Example 9 - Mixture Example

向列型LC主體混合物N1如下調配： The nematic LC host mixture N1 is blended as follows:

將0.3%之獲自實例1至6之可聚合單體化合物添加至LC混合物N1中，且將所得混合物引入VA－e/o測試單元(在90°下摩擦，對準層VA－聚醯亞胺，層厚度d4 μm)。在施加10 V電壓(交流電)下，將各單元用具有28 mW/cm² 強度的UV光照射20分鐘，促使單體化合物聚合。在第二組實驗中，另將0.006%之光引發劑Irgacure 651添加至LC/單體混合物中，且將曝光時間縮短至2分鐘。UV照射之前及之後，經由旋轉晶體實驗(Autronic－Melchers TBA－105)測定傾角。0.3% of the polymerizable monomer compounds obtained from Examples 1 to 6 were added to the LC mixture N1, and the resulting mixture was introduced into a VA-e/o test unit (friction at 90°, alignment layer VA-polyazide) Amine, layer thickness d 4 μm). Each unit was irradiated with UV light having an intensity of 28 mW/cm ² for 20 minutes under application of a voltage of 10 V (alternating current) to promote polymerization of the monomer compound. In the second set of experiments, another 0.006% of the photoinitiator Irgacure 651 was added to the LC/monomer mixture and the exposure time was shortened to 2 minutes. The tilt angle was measured by a rotary crystal experiment (Autronic-Melchers TBA-105) before and after UV irradiation.

為對比目的，用獲知於先前技術之不含間隔基的結構類似可聚合化合物(A)、(B)及(C)進行上述實驗。For the purpose of comparison, the above experiment was carried out using structures similar to the polymerizable compounds (A), (B) and (C) which were known to have no spacers in the prior art.

結果總結於表1中。The results are summarized in Table 1.

如由表1可見，與本發明之單體(1)－(6)聚合之後、尤其在不使用光引發劑的情況下，亦可達成足夠大的傾斜(亦即小傾角)。As can be seen from Table 1, a sufficiently large tilt (i.e., a small tilt angle) can be achieved after polymerization of the monomers (1) to (6) of the present invention, especially without the use of a photoinitiator.

本發明之化合物(1)－(6)因其優良溶解度(參見實例8)而特別適用於PS(A)顯示器中。The compounds (1) to (6) of the present invention are particularly suitable for use in a PS (A) display because of their excellent solubility (see Example 8).

實例10－混合物實例Example 10 - Mixture Example

由99.00%向列型LC主體混合物N2組成的LC介質 LC medium consisting of 99.00% nematic LC host mixture N2

0.25%之獲自實例6之可聚合單體化合物，及0.75%之對掌性摻雜劑S－4011適用於PS－VA顯示器中。0.25% of the polymerizable monomer compound obtained from Example 6, and 0.75% of the palmitic dopant S-4011 were suitable for use in a PS-VA display.

實例11－混合物實例Example 11 - Mixture Example

由99.00%向列型LC主體混合物N2(參見實例10)、0.25%之獲自實例7之可聚合單體化合物及0.75%對掌性摻雜劑S－4011組成的LC介質適用於PS－VA顯示器中。LC medium consisting of 99.00% nematic LC host mixture N2 (see Example 10), 0.25% of the polymerizable monomer compound obtained from Example 7, and 0.75% of palmitic dopant S-4011 is suitable for PS-VA In the display.

實例12－混合物實例Example 12 - Mixture Example

由99.50%向列型LC主體混合物N2(參見實例10)、0.25%之獲自實例6之可聚合單體化合物及0.25%對掌性摻雜劑S－5011組成的LC介質適用於PS－VA顯示器中。LC medium consisting of 99.50% nematic LC host mixture N2 (see Example 10), 0.25% of the polymerizable monomer compound obtained from Example 6, and 0.25% of the palmitic dopant S-5011 is suitable for PS-VA In the display.

實例13－混合物實例Example 13 - Mixture Example

由99.50%向列型LC主體混合物N2(參見實例10)、0.25%之獲自實例7之可聚合單體化合物及0.25%對掌性摻雜劑S－5011組成的LC介質適用於PS－VA顯示器中。LC medium consisting of 99.50% nematic LC host mixture N2 (see Example 10), 0.25% of the polymerizable monomer compound obtained from Example 7, and 0.25% of the palmitic dopant S-5011 is suitable for PS-VA In the display.

Claims

一種含有液晶原性及兩個或兩個以上可聚合基團之可聚合化合物在PS(聚合物穩定化)或PSA(聚合物持續對準)型液晶(LC)顯示器中的用途，其中至少一可聚合基團經由間隔基與該液晶原性連接且其中至少一可聚合基團不經由間隔基與該液晶原性連接，其中該等可聚合化合物係選自式I：P^a-Sp-A¹-(Z¹-A²)_m1-P^b I其中該等個別基團具有以下含義：P^a及P^b 彼此獨立地各自表示可聚合基團；Sp 表示間隔基；A¹及A² 彼此獨立地各自表示較佳具有4至25個C原子、亦可含有稠環且亦可經L單取代或多取代的芳族、雜芳族、脂環族或雜環基團；L 表示H、OH、鹵素、SF₅、NO₂、碳基團或烴基團；Z¹ 在各自出現時相同或不同地表示-O-、-S-、-CO-、-CO-O-、-OCO-、-O-CO-O-、-OCH₂-、-CH₂O-、-SCH₂-、-CH₂S-、-CF₂O-、-OCF₂-、-CF₂S-、-SCF₂-、-(CH₂)_n1-、-CF₂CH₂-、-CH₂CF₂-、-(CF₂)_n1-、-CH=CH-、-CF=CF-、-C≡C-、-CH=CH-COO-、-OCO-CH=CH-、CR⁰R⁰⁰或單鍵；R⁰及R⁰⁰ 彼此獨立地各自表示H或具有1至12個C原子的烷基；m1 表示0、1、2、3或4；n1 表示1、2、3或4。 Use of a polymerizable compound containing liquid crystal originality and two or more polymerizable groups in a PS (polymer stabilization) or PSA (polymer continuous alignment) type liquid crystal (LC) display, at least one of The polymerizable group is bonded to the liquid crystal via a spacer and wherein at least one polymerizable group is not bonded to the liquid crystal via a spacer, wherein the polymerizable compound is selected from the group consisting of Formula I: P ^a -Sp-A ¹ -(Z ¹ -A ² ) _m1 -P ^b I wherein the individual groups have the following meanings: P ^a and P ^b each independently represent a polymerizable group; Sp represents a spacer; A ¹ and A ² are each other Each independently represents an aromatic, heteroaromatic, alicyclic or heterocyclic group which preferably has 4 to 25 C atoms, may also contain a fused ring and may also be mono- or polysubstituted by L; L represents H, OH, halogen, SF ₅ , NO ₂ , carbon group or hydrocarbon group; Z ¹ represents the same or different -O-, -S-, -CO-, -CO-O-, -OCO-, -O-CO-O-, -OCH ₂ -, -CH ₂ O-, -SCH ₂ -, -CH ₂ S-, -CF ₂ O-, -OCF ₂ -, -CF ₂ S-, -SCF ₂ -, -(CH ₂ ) _n1 -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -(CF ₂ ) _n1 -, -CH=CH-, -CF=CF-, -C≡C-, -CH=CH-COO-, -OCO-CH=CH-, CR ⁰ R ⁰⁰ or a single bond; R ⁰ and R ⁰⁰ are independent of each other Each represents H or an alkyl group having 1 to 12 C atoms; m1 represents 0, 1, 2, 3 or 4; n1 represents 1, 2, 3 or 4.

如請求項1之用途，係用於含有一LC單元之PS型或PSA型LC顯示器中，該LC單元由以下各者組成：兩個基板，其中至少一基板可透光且至少一基板具有電極層；及一定位於該等基板之間、包含聚合組分及低分子量組分的LC介質層，其中該聚合組分可藉由在施加電壓下、使該LC介質中之一或多種可聚合化合物在該LC單元之該等基板之間聚合而獲得，其中該等可聚合化合物中至少一者為如請求項1之化合物。 The use of claim 1 is for a PS type or PSA type LC display including an LC unit, the LC unit being composed of two substrates, at least one of which is transparent and at least one of which has an electrode a layer; and an LC dielectric layer between the substrates, comprising a polymeric component and a low molecular weight component, wherein the polymeric component is capable of causing one or more polymerizable compounds in the LC medium by applying a voltage Obtained by polymerization between the substrates of the LC unit, wherein at least one of the polymerizable compounds is a compound of claim 1.

如請求項1之用途，其特徵在於，A¹、A²、Z¹、Sp及m1具有如請求項1中所指明之含義，且A¹及A² 彼此獨立地各自表示1,4-伸苯基、萘-1,4-二基或萘-2,6-二基，此外，其中該等基團中之一或多個CH基團可經N、環己烷-1,4-二基置換；此外，其中一或多個非相鄰CH₂基團可經O及/或S、1,4-伸環已烯基、二環[1.1.1]戊烷-1,3-二基、二環[2.2.2]辛烷-1,4-二基、螺[3.3]庚烷-2,6-二基、哌啶-1,4-二基、十氫萘-2,6-二基、1,2,3,4-四氫萘-2,6-二基、茚滿-2,5-二基或八氫-4,7-甲橋茚滿-2,5-二基置換，其中所有該等基團可未經取代或經L單取代或多取代； L 表示P-、P-Sp-、OH、CH₂OH、F、Cl、Br、I、-CN、-NO₂、-NCO、-NCS、-OCN、-SCN、-C(=O)N(R^x)₂、-C(=O)Y¹、-C(=O)R^x、-N(R^x)₂、視需要經取代之矽烷基、具有6至20個C原子之視需要經取代之芳基，或具有1至25個C原子之直鏈或支鏈烷基、烷氧基、烷基羰基、烷氧基羰基、烷基羰氧基或烷氧基羰氧基，此外，其中一或多個H原子可經F、Cl、P-或P-Sp-置換；P 表示可聚合基團；Y¹ 表示鹵素；R^x 表示P-、P-Sp-、H、鹵素、具有1至25個C原子之直鏈、支鏈或環狀烷基，此外，其中一或多個非相鄰CH₂基團可以O及/或S原子彼此間不直接相連之方式經-O-、-S-、-CO-、-CO-O-、-O-CO-、-O-CO-O-置換，且此外，其中一或多個H原子可經以下基團置換：F、Cl、P-或P-Sp-、具有6至40個C原子之視需要經取代之芳基或芳氧基，或具有2至40個C原子之視需要經取代之雜芳基或雜芳氧基。 The use of claim 1, characterized in that A ¹ , A ² , Z ¹ , Sp and m1 have the meanings as specified in claim 1, and A ¹ and A ² each independently represent 1,4-extension Phenyl, naphthalene-1,4-diyl or naphthalene-2,6-diyl, in addition, wherein one or more CH groups of the groups may be via N, cyclohexane-1,4-di In addition, one or more non-adjacent CH ₂ groups may be via O and/or S, 1,4-cyclohexenylene, bicyclo[1.1.1]pentane-1,3-di Base, bicyclo[2.2.2]octane-1,4-diyl, spiro[3.3]heptane-2,6-diyl, piperidin-1,4-diyl, decahydronaphthalene-2,6 -diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, indane-2,5-diyl or octahydro-4,7-methyl bridge indole-2,5-di Substituent substitution wherein all such groups may be unsubstituted or monosubstituted or polysubstituted by L; L represents P-, P-Sp-, OH, CH ₂ OH, F, Cl, Br, I, -CN, - NO ₂ , -NCO, -NCS, -OCN, -SCN, -C(=O)N(R ^x ) ₂ , -C(=O)Y ¹ , -C(=O)R ^x , -N(R ^x ) ₂ , an optionally substituted decyl group, an optionally substituted aryl group having 6 to 20 C atoms, or a linear or branched alkyl group having 1 to 25 C atoms, an alkoxy group, or an alkane Base carbonyl a group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkoxycarbonyloxy group, furthermore, wherein one or more H atoms may be substituted by F, Cl, P- or P-Sp-; P represents a polymerizable group Y ¹ represents halogen; R ^x represents P-, P-Sp-, H, halogen, a linear, branched or cyclic alkyl group having 1 to 25 C atoms, and further, one or more of them are non-adjacent The CH ₂ group may be O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- in such a manner that O and/or S atoms are not directly connected to each other. Substituting, and furthermore, wherein one or more H atoms may be substituted by: F, Cl, P- or P-Sp-, optionally substituted aryl or aryloxy having 6 to 40 C atoms Or a heteroaryl or heteroaryloxy group optionally having 2 to 40 C atoms.

如請求項1之用途，其中Sp係選自-(CH₂)_p1-、-O-(CH₂)_p1-、-OCO-(CH₂)_p1-或-OCOO-(CH₂)_p1-，且p1為1至12之整數。 The use of claim 1, wherein the Sp is selected from the group consisting of -(CH ₂ ) _p1 -, -O-(CH ₂ ) _p1 -, -OCO-(CH ₂ ) _p1 - or -OCOO-(CH ₂ ) _p1 -, And p1 is an integer from 1 to 12.

如請求項1之用途，其特徵在於，該等可聚合化合物係選自以下子式：其中P及Sp在各自出現時相同或不同地具有如請求項1或3中所指明之含義，L具有如請求項1及3中所指明之含義之一，L'及L"彼此獨立地各自表示H、F或Cl，Z在各自出現時相同或不同地具有如請求項1中針對Z¹所指明之含義之一且較佳表示-COO-、-OCO-或單鍵，x為0或1，r為0、1、2、3或4，s為0、1、2或3，且t為0、1或2。 The use of claim 1, wherein the polymerizable compounds are selected from the following subtypes: Wherein P and Sp have the same or different meanings as specified in claim 1 or 3 when they appear, L has one of the meanings indicated in claims 1 and 3, and L' and L" are independent of each other. Representing H, F or Cl, Z having the same or different meanings as indicated for Z ^{1 in} claim 1 and preferably representing -COO-, -OCO- or a single bond, x being 0 or 1, r is 0, 1, 2, 3 or 4, s is 0, 1, 2 or 3, and t is 0, 1 or 2.

如請求項2之用途，其特徵在於，該LC介質進一步包含一或多種下式化合物：其中該等個別基團具有以下含義：a 表示1或2；b 表示0或1；表示或R¹及R² 彼此獨立地各自表示具有1至12個C原子的烷基，此外，其中一或兩個非相鄰CH₂基團可以O原子彼此間不直接相連之方式經-O-、-CH=CH-、-CO-、-OCO-或-COO-置換；Z^x 表示-CH=CH-、-CH₂O-、-OCH₂-、-CF₂O-、-OCF₂-、-O-、-CH₂-、-CH₂CH₂-或單鍵，較佳表示單鍵；L^1-4 彼此獨立地各自表示F、Cl、OCF₃、CF₃、CH₃、CH₂F、CHF₂。 The use of claim 2, characterized in that the LC medium further comprises one or more compounds of the formula: Wherein the individual groups have the following meanings: a represents 1 or 2; b represents 0 or 1; Express or R ¹ and R ² each independently represent an alkyl group having 1 to 12 C atoms, and further, one or two non-adjacent CH ₂ groups may be O-, in such a manner that O atoms are not directly connected to each other. -CH=CH-, -CO-, -OCO- or -COO-substitution; Z ^x represents -CH=CH-, -CH ₂ O-, -OCH ₂ -, -CF ₂ O-, -OCF ₂ -, -O-, -CH ₂ -, -CH ₂ CH ₂ - or a single bond, preferably a single bond; L ^1-4 independently of each other represents F, Cl, OCF ₃ , CF ₃ , CH ₃ , CH ₂ F , CHF ₂ .

如請求項2之用途，其特徵在於，該LC介質進一步包含一或多種下式化合物：其中該等個別基團具有以下含義：表示，，，表示或，R³及R⁴ 彼此獨立地各自表示具有1至12個C原子的烷基，此外，其中一或兩個非相鄰CH₂基團可以O原子彼此間不直接相連之方式經-O-、-CH=CH-、-CO-、-OCO-或-COO-置換；Z^y 表示-CH₂CH₂-、-CH=CH-、-CF₂O-、-OCF₂-、-CH₂O-、-OCH₂-、-COO-、-OCO-、-C₂F₄-、-CF=CF-或單鍵。 The use of claim 2, characterized in that the LC medium further comprises one or more compounds of the formula: These individual groups have the following meanings: Express , , , Express or R ³ and R ⁴ each independently represent an alkyl group having 1 to 12 C atoms, and further, one or two non-adjacent CH ₂ groups may be via O- in a manner in which O atoms are not directly connected to each other. , -CH=CH-, -CO-, -OCO- or -COO-substitution; Z ^y represents -CH ₂ CH ₂ -, -CH=CH-, -CF ₂ O-, -OCF ₂ -, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -C ₂ F ₄ -, -CF=CF- or a single bond.

一種如請求項1至7中任一項所定義的LC顯示器。 An LC display as defined in any one of claims 1 to 7.

如請求項8之LC顯示器，其特徵在於，其為PSA-VA、PSA-OCB、PS-IPS、PS-FFS或PS-TN顯示器。 The LC display of claim 8, characterized in that it is a PSA-VA, PSA-OCB, PS-IPS, PS-FFS or PS-TN display.

一種LC介質，其包含：-包含一或多種可聚合化合物的可聚合組分A)；及-包含一或多種低分子量化合物的液晶組分B)，其中組分A)包含一或多種如請求項1至5中任一項所定義的可聚合化合物。 An LC medium comprising: - a polymerizable component A) comprising one or more polymerizable compounds; and - a liquid crystal component B) comprising one or more low molecular weight compounds, wherein component A) comprises one or more The polymerizable compound as defined in any one of items 1 to 5.

如請求項10之LC介質，其中組分B)包含一或多種如請求項6或7所定義的化合物。 The LC medium of claim 10, wherein component B) comprises one or more compounds as defined in claim 6 or 7.

一種用於製備如請求項10或11之LC介質的方法，其係將一或多種低分子量液晶化合物與一或多種如請求項1至7中任一項所定義之可聚合化合物混合，且視需要與其他液晶化合物及/或添加劑混合。 A method for preparing an LC medium according to claim 10 or 11, which is a method of mixing one or more low molecular weight liquid crystal compounds with one or more polymerizable compounds as defined in any one of claims 1 to 7, and It needs to be mixed with other liquid crystal compounds and/or additives.